Plastics Materials

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Plastics Materials
Properties and Applications
Second Edition
A.W. BIRLEY
R.J.HEATH
Institute of Polymer Technology and Materials Engineering
University of Technology
Loughborough, UK
M.J. SCOTT
Lowe & Fletcher Ltd
Telford, UK
BLACKIE ACADEMIC & PROFESSIONAL

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First edition 1982

Second edition 1988
Reprinted 1994
© 1988 B1ackie & Son Ltd
Typeset by Thomson Press (India) Ltd, New Delhi
ISBN 978-0-7514-0162-2 ISBN 978-94-011-7614-9 (eBook)

DOl 10.1007/978-94-011-7614-9
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Preface
Plastics are part of everyday life and contribute immensely to the benefit
of humanity. When failures occur, they are due in part either to inferior
properties (resulting from poor design or badly controlled processing), or
to an incomplete understanding of the properties and applications of
plastics materials.
Since publication of the first edition, the plastics industry has increas-
ingly adopted advanced business procedures and automation (such as
closed loop control and robotics), to combat the effects of recession, and
has moved increasingly towards methods based on sound scientific and
technological principles. Plastics have increasingly been used in appli-
cations once dominated by the use of metals and ceramics. For instance, in
the automotive industry, the modern car now contains a much higher
proportion of polymers, including commodity plastics and more spec-
ialized materials. In addition, compact discs are being made from new
injection-moulding grades of polycarbonate, which meet the requirements
of a demanding process.
This second edition has been thoroughly revised and extended to
include new materials, technologies and design concepts. Chapters on
thermoplastics reflect the development of polymer blends and alloys,
whilst the chapters devoted to thermosets have been reorganized to
accommodate the renaissance in the applications of phenolics and to
cover the growing importance of polyurethanes. The related two-
component process technologies are now included; having undergone
major developments in the last decade, they have become important
shaping processes.
We hope that readers, whether new to or experienced in plastics
technology, will find in this book something that will extend their
knowledge and increase their understanding of the field.
AWB
RJH
MS
Contents
1 Introduction 1
1.1 Background 1
1.2 Structure and properties of plastics I
1.2.1 Mechanical properties 2
1.2.2 Thermal properties 3
1.2.3 Electrical properties 5
1.2.4 Optical properties 5
1.2.5 Melt properties 5
1.2.6 Chemical properties 6
1.3 Additives 7
1.4 Processing of plastics 8
1.4.1 Thermoplastics processing 8
1.4.2 Foams 9
1.4.3 Shaping of cross-linking plastics 9
1.5 Practical methods of processing 10
1.5.1 Thermoplastics processing 10
1.5.2 Processing methods for cross-linking plastics 16
1.6 Interactions between shaping process and plastics materials 20
Further reading 21
2 Fundamentals of design 23
2.1 Engineering design 23
2.1.1 Fracture mechanics applied to plastics 30
2.2 Design limitations imposed by processing method 33
2.3 Product design 35
2.3.1 Thermoplastics 35
2.3.2 Thermosetting plastics 35
2.3.3 Foams and reinforced plastics 36
2.3.4 Tolerance and dimensional control of products 39
2.4 Importance of economics of processing in design 40
Further reading 46
3 Styrene plastics 47
3.1 Polystyrene 47
3.2 High impact polystyrene 49
3.3 Styrene copolymers 52
3.4 ABS plastics 54
3.5 Polystyrene-poly(phenylene oxide) blends 56
4 Other amorphous thermoplastics 60

4.1 Poly(methyl methacrylate) 60
4.2 Cellulose plastics 64
4.2.1 Regenerated cellulose 64
4.2.2 Cellulose esters 65
4.2.3 Cellulose ethers 66
4.3 Polycarbonates 66
viii CONTENTS
5 Propylene plastics 72
5.1 Homopolymer and impact-modified grades 72
5.2 Filled polypropylene 83
5.3 Foamed polypropylene 84
5.4 Miscellaneous applications of propylene polymers 86
6 Other polyolefin plastics 87

6.1 Polyethylene 87
6.1.1 High-density polyethylene 88
6.1.2 Low-density polyethylene 92
6.1.3 Linear low-density polyethylene 94
6.1.4 Very low-density polyethylene 95
6.1.5 Blends of ethylene polymers 95
6.2 Ethylene copolymers 100
6.3 Polybut-1-ene 100
6.4 Poly-4-methylpent-1-ene 101
7 Other crystalline thermoplastics 103

7.1 Polyamides 103
7.1.1 General-purpose polyamides 103
7.1.2 Modified polyamides 106
7.1.3 Aromatic polyamides and polyimides 111
7.2 Thermoplastic polyesters 111
7.2.1 Homo-polyesters 111
7.2.2 Blends of polyesters 116
7.3 Polyacetals 117
8 Vinyl chloride plastics 124

8.1 Un plasticized poly(vinyl chloride) 124
8.2 Plasticized poly(vinyl chloride) 128
8.3 Vinyl chloride copolymers 132
8.4 Blends of poly(vinyl chloride) 133
8.5 Vinylidene chloride polymers and copolymers 133
9 Speciality therntoplastics 135

9.1 Fluoroplastics 135
9.1.1 Poly(tetrafluoroethylene) 135
9.1.2 Poly(vinylidene fluoride) 138
9.1.3 Other fluoropolymers 140
9.2 Polysulphones 140
9.3 Poly(phenylene sulphide) 144
10 Cross-linked plastics 148

10.1 Introduction 148
10.2 Phenol-formaldehyde plastics 149
10.2.1 Novolak PF resins 151
10.2.2 Resol PF resins 156
10.3 Urea-formaldehyde plastics 158
10.4 Melamine-formaldehyde plastics 161
10.5 Unsaturated polyester resins 163
10.5.1 Structure and properties 164
10.5.2 Glass fibre-reinforced polyesters 164
10.6 Epoxide resins 170
11 Polyurethane plastics 174

11.1 Introduction 174
11.2 Molecular structure-property relationships 175
CONTENTS ix
11.2.1 Typical reactions 175
11.2.2 Monomeric components 176
11.3 Properties and applications of polyurethanes 180
11.3.1 Flexible polyurethane foams 180
11.3.2 Rigid polyurethane and polyisocyanurate foams 182
11.3.3 Reaction injection moulded polyurethane products 184
11.3.4 Elastomeric and resinous thermosetting polyurethanes 189
11.3.5 Thermoplastic polyurethanes 190
11.3.6 Polyurethanes as surface coatings, adhesives and sealants 191
Further reading 192
Index 193
1 Introduction
1.1 Background
Many plastics are now used in such quantities that they have reached the
status of commodity materials; indeed, the volume usage of plastics now
comfortably exceeds that of metals. Much of the growth has taken place over
the last thirty-five years, and the plastics industry is still expanding at twice the
rate of the economy as a whole. The motivation for the rapid growth is the
suitability of plastics for mass production, which depends mainly on their easy
and reproducible shaping, and their low volume cost, coupled with some
attractive properties. Shaping at low temperatures into complex forms is a
characteristic of most plastics, and ensures their increasing use in spite of some
shortcomings. The manufacturing industry has responded very positively to
the increasing demand for plastics and for diversification of properties. The
major feedstock is oil; the dependent petrochemicals industry supplies the
monomers for plastics production, and manufactures a wide range of additives
to modify their behaviour.
The principal structural feature of most plastics is that a unit, or mer, is
linked chemically many times (poly). The chemical process for the formation of
such materials is known as polymerization and the products are polymers.
Plastics cannot be defined precisely, although they are undoubtedly polymers
and, by dictionary definition, they must be capable of being shaped at some
stage in their history. Plastics are generally rigid, in contradistinction to
rubbers (elastomers), which are very flexible.
1.2 Structure and properties of plastics

There are two subgroups of plastics: thermoplastics and cross-linked plastics.
The former are linear chain polymers which soften on heating and solidify
again on cooling, whereas the latter are network structures (in three
dimensions) which, once formed, are not softened by heating. The repetition of
units in a polymer can result in a regularity of structure which may have
important consequences; in favourable cases a number of chains may become
aligned and in register for some distance, a state which is favoured on energy
grounds, and which is termed crystallinity. The occurrence of crystallinity in a
polymer affects profoundly both processing and properties, and will be
referred to frequently in the later chapters of this book.
2 PLASTICS MATERIALS
'Properties' provide quantitative information on the response of a material

to external stimuli, which can be mechanical, thermal, electrical, optical,
chemical, etc., or combinations of these. Thus, if a material is stressed
mechanically, it responds by deforming or breaking, the relevant properties
being 'modulus' or 'strength'. Application of thermal energy to a sample causes
it to increase in temperature, the relationship being termed the 'enthalpy' or
'heat content', and to increase its dimensions ('thermal expansion'). Consider-
ation of the properties of plastics allows a first-order distinction to be made
between those properties which depend on the organic nature (involving the
element carbon), and which are based on short-range interactions, particularly
the repeat unit, and those which result from the long-chain or network
structure. The former include density, dielectric permittivity, melting and
softening temperatures, and the interaction with solvents, acids and bases. The
polymeric nature leads to properties which are unique, exemplified by the very
high viscosities of solutions and melts of linear polymers, and the accommod-
ation of very high deformation without fracture, with the possibility of almost
complete recovery on removing the stress. In view of the great importance of
the chain length or molecular weight of a polymer, many methods have been
developed for its determination; quality control by molecular-weight (MW)
measurement is now not uncommon. Monitoring MW-dependent properties,
such as melt viscosity, is still practised widely.
In a more detailed consideration of properties, there is interaction between
those dependent on short-range interactions and, in particular, the nature of
the repeat unit in the polymer and the constraints imposed by the chain or
network structure. For example, the density of a plastic is that expected of an
organic substance (0.8 to 1.4 Mg m - 3). On cooling, the material changes density
continuously as it strives towards equilibrium, but is constrained by the poly-
mer structure. This time dependence is characteristic of polymers, particularly
thermoplastics, and is a factor of considerable importance in their technology.
Properties are determined for many reasons, ranging from assurance of the
quality of a product to providing the basis for component design and
predicting its service life. These different requirements lead to different test
philosophies, for quality control is concerned with the reproducibility of a
simple, cheap but discriminating test procedure for fixed (but arbitrary) test
parameters, while data for design are required over wide ranges of important
variables, and are thus much more expensive to obtain. This book will be
mainly concerned with design data and their application: an important source
of information is BS 4618, Recommendations for the Presentation of Design
Data for Plastics (British Standards Institution, London).
1.2.1 Mechanical properties

Adequate mechanical properties are a prerequisite in most applications of
plastics; response to stressing by fracture or deformation is usually of crucial
INTRODUCTION 3
importance, while friction, wear, vibration damping etc., may be relevant in
particular applications. For metals, it is commonly accepted that the
behaviour can be forecast by stress analysis, thence using the modulus or
design stress in the appropriate formula. A similar procedure has been shown
to be applicable to plastics for stiffness in closely controlled experiments on
carefully selected structural elements which are homogeneous and isotropic,
provided that the appropriate value of 'modulus' is employed. This will be
exemplified and discussed in the next chapter.
Breakage of a component or article is frequently a limitation on its use; this
subject has, therefore, received considerable attention. Failure may be brittle
or ductile, the former occurring at low elongation, the latter with considerable
deformation, and as the culmination of creep. Brittle failure in plastics
materials is sometimes inherent and sometimes unexpected. Many laboratory
tests indicate that most plastics are either tough or brittle, which is very
convenient, since there are rules for dealing with ductile materials, and
different rules for dealing with brittle ones. However, some plastics break at
unexpectedly low stresses and, even more seriously, products made from
plastics which are expected to be ductile from laboratory tests and general
experience can also fail in a brittle manner.
Considerations based on a fracture mechanics analysis are necessary if the
designer is to progress beyond the primary division of plastics into 'ductile' or
'brittle', based on simple laboratory tests (see Chapter 2).
1.2.2 Thermal properties

The thermal properties of plastics are generally those expected for organic
substances, modified in some cases by the polymer structure. Thus, partially
500
400
naphtha lene
.-
-..C> .,.'
2-
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300 .' .
. " ..
Co
.- ;'
co ( ;'
... ..
.r:.
.- ..
.,
E 200
.- ... .. polycarbonate
100
0
50 100 150 200
temperature ( · C )
Figure 1.1 Enthalpy (heat content) vs. temperature. Comparison of data for typical crystalline
material (naphthalene) with those for crystalline (acetal copolymer) and amorphous (poly-
carbonate) plastics
crystalline plastics have melting points, although the fusion process is gradual.
Thermal conductivity is low; conversely, thermal expansion and contraction
are high. The relationship between heat energy applied and the resulting rise in
temperature, the enthalpy or heat content, is generally as expected.
Thermal properties are relevant both to processing and to behaviour in the
solid state. For partially crystalline plastics, the melting temperature defines
the upper limit of form stability, although the plastic may soften unacceptably
at lower temperatures. In processing, the enthalpy defines the quantity of heat
which is necessary to change the temperature from ambient to the processing
temperature. For crystalline plastics this will include a substantial contri-
bution from the latent heat of fusion of the crystalline phase; indeed, the heat
content at the processing temperature may well be a factor of two higher for a
crystalline plastic compared with an amorphous one. It must be remembered
that this heat has to be supplied during the heating stage and, more
importantly, removed during cooling. This is illustrated in Figure 1.1, where
data for a partially crystalline plastic, (acetal copolymer), are compared with
those for an amorphous polymer (polycarbonate), and a crystalline low-
molecular-weight organic material (naphthalene).
Differences between crystalline and amorphous plastics can be found also in
thermal expansion and contraction, where the generally enhanced density of
the crystalline regions results in greater differences between melt- and solid-
phase densities, and aggravation ofthe mould shrinkage problem, (Figure 1.2).
The heating and cooling of plastics masses is retarded by their low thermal
conductivities, causing these operations to be time-dominating in many
processes; for example, thermal conductivity of copper is 385 W m - 1 K - 1,
that of polypropylene, 0.2 W m - 1 K -1, whereas cellular polymers have
excellent insulation properties, 0.02 W m -1 K - 1 for rigid polyurethane foam.
0·7 1·30
PVC
I pp
Ci 0·7 I
E
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PVC I
.§. I
I
~ 0·7 I 1·20
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50 100 150 200
Figure 1.2 Thermal expansion of crystalline (polypropylene) and amorphous (poly(vinyl-
chloride)) plastics
INTRODUCTION 5
1.2.3 Electrical properties
As would be expected from their structures, most plastics, at least in the solid
state, are very poor conductors of electricity; indeed, some are amongst the
best insulators known. Dielectric properties-relative permittivity and power
factor (or loss factor)-are typical of those found in low-molecular-weight
organic materials, although the fine structure of such properties is affected by
features associated with the structure. Conversely, the measurement of
dielectric properties, which can be made with high precision over very wide
frequency ranges, provides a powerful means of probing polymer structure.
The insulation afforded by plastics materials with the poorest properties,
such as polyamide 6.6 or plasticized PVC, is still more than adequate, except
for the most critical uses. This is exemplified by the use of the former by British
Rail as an in sui ant in automatic track signalling, and of the latter in domestic
cable insulation.
The intrinsic electrical strength of most plastics is higher by a factor of a
thousand than the breakdown strength of air, so that in most practical
situations breakdown is dominated by the breakdown of the air.
1.2.4 Optical properties

While the refractive properties are not unusual, covering a refractive index
range of 1.35-1.65 for solid (unfoamed) materials, the transparency can vary
considerably: some plastics are almost perfectly transparent, and find
application as optical components, whereas others are translucent or opaque.
The difference in transparency depends on the microstructure; scattering of
light occurs from multiphase structures, the phases differing in refractive index
and being of a size comparable with the wavelength oflight. Scattering oflight
and a consequent deterioration in transparency can also result from surface
irregularities, again on the scale of the wavelength of light, which can be
introduced during processing. Such surface structure is frequently associated
with haziness in polyethylene packaging film. A further aspect of surface
scattering is a decrease in the gloss.
Colour is another aspect of optical properties, but here, plastics do not
introduce any new phenomena, rather it is the behaviour of the colourants
which is of interest: they must be stable during processing and use, and should
not induce any reaction, either physical or chemical, in the polymer. It has
been observed that for partially crystalline polymers, colourants frequently
behave as nucleating agents.
1.2.5 Melt properties

As noted previously, the widespread use of plastics is based on the ease with
which they can be shaped. Thermoplastics are rendered tractable by the
application of heat, the shaped part being stabilized in form by cooling; no

chemistry is involved. Cross-linking plastics, on the other hand, are shaped as
comparatively low-molecular-weight prepolymers, stabilization of shape
being achieved by cross-linking by specific chemical reactions. For both
classes of plastics, the ease of shaping is related to the fluidity of the material:
the mobility of pre polymers and the high viscosity ofthermoplastics both limit
the range of processing techniques which can be applied. Processing will be
treated in greater detail later in this chapter.
1.2.6 Chemical properties

These may be subdivided into physical phenomena and those where there is
chemical reaction: the former include the transmission of fluids through
plastics barriers (permeation), and the interaction of plastics with solvents,
the effects ranging from swelling to solution. Chemical reaction causes
permanent change to the polymer.
The low density of plastics implies a relatively open structure which can be
penetrated by fluids, such as water, oxygen or carbon dioxide, during which
the barrier material may be affected only marginally. Permeation is especially
important in packaging.
The interaction of plastics with solvents is relevant to the wider use of
plastics materials. Solution (for linear polymers) or maximum swelling (for
cross-linked systems) is favoured by similarity between polymer repeat unit
and the solvent, and by specific interaction between solvent and polymer. On
the other hand, solubility is reduced by crystallinity in the plastic, the energy
associated with the formation of the crystallites having to be overcome before
solution can be effected. Thus, crystalline plastics are considerably more
resistant to solvents than are amorphous materials.
Although plastics are not particularly reactive chemically, and some are
distinctly inert, the extent of chemical changes in plastics is useful information
for the designer. An important class of reactions is that associated with ageing,
which, as the term implies, is deterioration in performance which is progressive
with time. Further, some environments are aggressive towards plastics, for
example, strongly oxidizing liquids such as hot, fuming nitric acid. Other less
powerful reagents promote premature brittle failure in plastics components
under stress, a phenomenon known as environmental stress cracking.
The ageing of plastics can be the result of physical change or chemical
reaction; the former includes the reorganization of crystal structure, free
volume changes and material redistribution, such as the migration of
plasticizer. Chemical ageing is very dependent on the environment, especially
on temperature, oxygen, ozone, moisture, light (particularly ultraviolet
radiation), and sometimes on biological factors. More than one of these
agencies may be operative, leading to enhanced activity: for example,
oxidation reactions are accelerated at high temperatures. Although some
INTRODUCTION 7
ageing processes progress inexorably, and can only be minimized by the
elimination of factors which would worsen their effects, the incidence of other
ageing phenomena can be reduced dramatically by certain additives. Antioxi-
dants, to reduce oxidation, and UV stabilizers to protect against the effects of
this radiation, are examples of great commercial importance.
1.3 Additives
Reference has already been made to antioxidants and UV stabilizers; these
exemplify an important branch of plastics technology, the use of additives to
modify the behaviour. Some additives are employed only in small con-
centration (0.1-1 %), and are effective at this level, whereas others may
constitute the major part of a plastics composition, being used, for example, to
enhance the rigidity, or to reduce the cost. Additives used in low concentration
include antioxidants, UV stabilizers, lubricants (to facilitate processing), slip
and anti-blocking additives for film-surface modification, dyes and pigments.
Additives used mainly to improve mechanical properties or economics include
particulate fillers, fibres and gases, the last resulting in foams. Dispersion of
particles of a solid with modulus higher than that of the plastics matrix
inevitably results in a composite of higher rigidity. The increase in rigidity is
smallest for fillers of spherical shape, and greatest for those of high aspect ratio,
particularly long fibres. For all fillers the effects are proportional to the
volume fraction of the additive and, as well as mechanical properties,
improvements in dimensional stability and reduced thermal expansion and
contraction are observed. Conversely, some additives are used to reduce the
stiffness, notably plasticizers and rubbers.
Recently there has been increased use of surface coating materials, i.e.
printing inks, metallization, or painting, to enhance the appearance and
surface-related properties of plastics (e.g. barrier properties to gases or UV
radiation, or increased abrasion resistance). Usually such treatment is
accompanied by pretreatment to modify the surface of the polymer and to
ensure adhesion of the surface coating to the substrate.
Composites offer the designer a means of extending the usefulness of
plastics, but the behaviour can be very complex, requiring much more detailed
definition of the properties. Thus, whereas the deformation of an isotropic
material can be defined by two of the three moduli, anisotropic materials
require a minimum of five engineering moduli for adequate description. A
further disadvantage accruing from the use of composites is more difficult and
less predictable processing behaviour; in particular, the shear viscosity is
increased with filler content, even more than the modulus, and again, long
fibres are the most effective. Composites involving fibre reinforcement are
almost inevitably anisotropic in their properties. Commercially important
composites are included in the later chapters, where appropriate.
1.4 Processing of plastics

As noted previously, an important factor favouring the use of plastics in any
application is the easy shaping: for even the most recalcitrant polymer,
shaping can be accomplished at moderate temperatures with equipment
fabricated from conventional materials. There is the added advantage that
many of the shaping processes are suited to automatic operation.
1.4.1 Thermoplastics processing

Thermoplastics comprise the majority of the market for plastics materials;
their shaping will be discussed first. For the analysis of such processes, it is
helpful to consider a number of 'unit operations', which provide a framework,
or skeleton, on which the detail may be developed. The important stages are:
Melting
Mixing and homogenization
Melt transport
Primary shaping
Secondary shaping
Shape stabilization
Finishing operations.
These operations are usually carried out sequentially and some, such as
secondary shaping, may be omitted. Additional mixing may also be included,
e.g. powder blending, where mixing is partially achieved prior to melting;
however, final homogenization can only be attained by mixing in the molten
state.
Melting, mixing and homogenization are frequently accomplished by an
Archimedean screw rotating in a heated barrel, which is often an integral part
of the processing equipment. Alternatively, a plastics compound can be made
in a separate process, e.g. by batch operation in an internal mixer. Such a pre-
mixed compound reduces the problem of achieving good dispersion of the
components, but before shaping, the melt must also be at a uniform
temperature and have experienced similar shear history, so that it will respond
predictably and reproducibly in the subsequent shaping operations.
There are many ways of shaping a polymer melt, for example, a mould or an
extrusion die; calendering is a further possibility. In shaping, the rheological
properties of the polymer melt are relevant and determine the pressures
necessary to move the melt. The shear viscosity of the melt is important,
defining the shaping behaviour, and is frequently measured in quality-control
tests, e.g. the melt flow index (MFI). The elastic properties are also important
in shaping. Problems often arise due to interaction between the process and
the structure of the polymer. Thus, the extrusion of complex profiles still defies
accurate analysis, and most mouldings have residual strain, and possibly other
INTRODUCTION 9
defects, leading to anisotropic properties, which so far have not been predicted
quantitatively. Furthermore, the shear response of the melt is modified by
fillers and complicated by fibrous additives.
1.4.2 Foams
Foams are important because of their improved rigidity per unit weight,
compared with solid plastics, and for the ease and versatility of their
processing. In the design offoamed products, little advantage will be gained for
section thicknesses less than 6 mm, i.e. by using existing injection moulds.
Normal injection presses can be adapted for moulding foams, but they have
unnecessarily high locking forces, together with restricted platen areas and
plasticizing capacities. Polymer is injected into the cavity at low pressure and
allowed to foam; the resulting pressure is low, and the locking force required is
small. The platen size can be large, and large mouldings can be produced with
small locking forces. The plasticizing unit should be of high capacity, to
provide sufficient polymer melt for the shot. The special foam machines are
considerably cheaper and more economical to run than conventional
machines. The production of polyurethane foam materials is dealt with
separately.
1.4.3 Shaping of cross-linking plastics

The basic stages, or unit operations, for forming cross-linking plastics are
similar to those already considered for thermoplastics, but there are dif-
ferences in detail and, more important, these differences allow some of the
difficulties inherent in thermoplastics shaping to be circumvented. The
fundamental difference between the processing of thermoplastics and cross-
linking plastics is that, whereas chemistry is scrupulously avoided for the
former, it is required for the latter. Thus thermoplastics melts have high
viscosities, resulting from the high molecular weights necessary to achieve
satisfactory mechanical properties. Robust equipment and high forces for
manipulating the melt are necessary. By contrast, prepolymers for cross-
linking systems can be of relatively low molecular weight and therefore of low
melt viscosity; processing equipment can be lighter in construction, and forces
very much lower.
Referring again to the scheme of unit operations detailed earlier in this
section, the major difference between thermoplastics and cross-linking plastics
is the shape stabilization stage; for thermoplastics, this is achieved by cooling,
whereas for the latter, chemical reaction is involved, implying that the system
is frequently heated at this stage. The shape-stabilizing reaction is essentially
further polymerization carried out in the mould: heat is evolved and there is
frequently considerable shrinkage. High levels of filler are added to reduce
shrinkage and to cheapen the product; fibrous fillers and textiles are
particularly important and give composites of considerably enhanced pro-

perties. Glass fibres provide the usual fibrous reinforcement, although
asbestos still finds some application, and the newer carbon and Aramid™
fibres are used increasingly, often in mixed fibre systems. Cellulose fibres
contribute useful properties to composites, especially improving the impact
performance of PF mouldings.
1.5 Practical methods of processing
1.5.1 Thermoplastics processing

The techniques for primary shaping will be discussed first, to be followed by
consideration of the more important techniques of secondary shaping.
Extrusion is a continuous process which has the most economical output of
all plastics shaping methods. Extruded products are simple in shape and have
features in only two directions, being continuous in the third (extrusion),
direction. Common products manufactured by this process are pipe and other
rainwater goods, curtain rails, flat and tubular film, sheet, wire-covering and
fibres. The heart of this method is the screw, which consists of three sections,
fulfilling three functions: the feed and compression zone, the plasticizing zone,
and finally the metering section (Figure 1.3). Extruders may contain one, two,
or occasionally three separate screws in parallel.
Powder or granular material is fed from the hopper, through the throat and
on to the screw. Rotation of the screw transports the plastic along the cylinder
through the first zone, where it is compacted and trapped air is expelled.
Progressing down the cylinder, it is heated further by shear between the screw
hopper
sizing die cy li nder screw
L.. ,,;,g zonJ plasticizing

zon e
I feed and
co mpresSion zone
motor
Figure 1.3 Ex truder

INTRODUCTION 11
and the cylinder walls, and by conduction of heat from the wall, so that the
material is melted by the end of this zone. The final section of the extruder
ensures the consistent and required output of molten polymer. The melt
usually passes through a die, which defines a profile; this is cooled in air, or
more frequently, in a cooling bath. A 'sizing die' is often included in the cooling
train to rectify changes in profile of the extrudate after leaving the die.
Foams can be manufactured on standard extruders; the main problem being
to control the amount of foaming on leaving the extruder. This is usually
achieved with several sizing and cooling rollers. PVC foam for wood
replacement is becoming an important market.
(i) Injection moulding. Plastics material in granular or powder form is fed

into the injection cylinder from the hopper, and is transported forward by
rotation of the screw (Figure 1.4). Early injection presses used piston plungers
to transport the melt, but from 1967 onwards, injection units have had
reciprocating screw plungers. As the material moves down the cylinder, it is
heated by shear between the cylinder wall and the screw and by conduction
from the wall. (Band heaters are fitted to the outside of the cylinder). By
regulating the power to the heaters, and the amount of shear on the plastic, it is
uniform in temperature by the time it reaches the front end of the cylinder, and
forms the melt pool. As more material is transported forward to the melt pool,
the screw is forced backwards until a preset quantity of melt is available in the
melt pool; this is commonly known as the shot weight, or more correctly, the
shot volume. In spite of this, the shot weight is usually quoted, most frequently
in terms of polystyrene. It must be remembered that this value must be
corrected when the machine is moulding plastics other than PS, for example,
cavity injection cylinder
mou ld screw rotat ing unit
Figure 1.4 Injection moulder

the shot weight for PP is

density of PP
shot weight (PP) = shot weight (PS)·
density of PS
Thus the shot weight (PP) is some 15% smaller than that for PS.
The melt is then injected through the nozzle, sprue and runners into the
relatively cool mould cavity by the forward movement ofthe screw, acting as a
piston. Pressure is maintained on the melt while it cools in the cavity, until the
entrance to the mould (gate) has solidified. The pressure is released and the
screw starts rotating to prepare another shot, but the mould stays closed for
a further time to solidify the material in the cavity before the mould opens, and
the moulding is ejected. The mould then closes and the cycle is repeated.
Since most injection moulding machines can be run automatically, the
process is suited to the making of large quantities of similar shapings at low
cost. Complex mouldings may need retractable mould parts.
(ii) Calendering. This process was developed in the rubber industry, but
more recently, the plastics industry has adopted the method to produce sheet
or film, particularly from plasticized PVC. This is a process in which sheets or
films of uniform thickness are produced by squeezing the molten polymer
through a succession of rotating rolls. Modern calenders usually consist of
four rolls or cylinders, which are temperature-controlled, in an inverted 'L' or
inverted 'Z' configuration (see Figure 1.5). Molten polymer is fed to the first
pair of rolls from an internal mixer, two-roll mill or extruder, with the roll
separation controlling the feed rate. Subsequent roll separations (nips) refine
the final product thickness.
An outstanding feature of this process is the very high output for a
comparatively low energy input, compared with extrusion; further, it is
especially suitable for heat-sensitive materials. Calendering is used to produce
film and sheet, and for laminating plastics film to other substrates, including
other plastics films, textiles, paper and metal foil.
typical arrangement
of a four-roll calender
to embossing
and cooling units
/
Figure 1.5 Calender

INTRODUCTION 13
(iii) Rotational moulding. This process is best suited to hollow components
of simple shape, especially ifthey are required in small numbers, up to 1 000 per
year. The process has been used for the manufacture of dustbins, 3 m 3 storage
tanks, small huts for road-workers, and boat hulls; it is also used to fuse
plasticized PVC pastes, e.g. in the production of automotive parts, to include
crash pads and armrest skins. The technique involves, as the title suggests,
rotating a mould. The component is formed inside a hollow mould, which is
heated, whilst being rotated on two axes, mutually at right angles. Four stages
are involved in the moulding cycle: loading powder into the mould, melting
and shaping, cooling and extracting the finished moulding. When the powder
has been loaded into the cavity, the mould is closed, and it is heated and
rotated. Rotation speeds are low, rarely exceeding 40 rpm on the secondary
axis and 12 rpm on the primary axis. The mould is heated by air or oil, or by
directing gas jets on to its exterior. The powder melts, forming a homogeneous
layer of molten plastic on the inside of the mould, and becomes evenly
distributed over the surface through gravitational forces. The heating and
rotation are continued until all the powder has melted; the mould assembly is
then transferred to a cooling system, involving either water or forced air. After
solidification of the plastic, the mould is opened and the moulding removed.
Important methods of secondary shaping based on melt extrusion are outlined

below.
(iv) Tubular film. Most film is manufactured by this process, in which a tube
extruded vertically is simultaneously blown radially by introducing air into
the tube (under pressure), and extended longitudinally by nip rolls running at a
higher linear speed than the extrusion rate (see Figure 1.6). The nip rolls also
serve to prevent the immediate escape of the air pressurizing the radial blow.
The flow of air into the tube is controlled to give a constant bubble size and
thus a consistent film thickness. The film is flattened by the rolls and passes to a
wind-up unit.
(v) Extrusion blow moulding. Most small and medium-sized enclosed con-
tainers, such as bottles and small drums, are produced by this process; more
recently, complex shapes, including car fuel tanks and coolant reservoir tanks,
have been blow moulded.
A predetermined length of molten tubular extrudate, known as a parison, is
introduced into an open mould (Figure 1.7). On closing the mould, the parison
is trapped and welded at the top and bottom; air is then injected into the tube
which is expanded and takes the shape of the cavity within the mould. Air
pressure is maintained, keeping the moulding in contact with the cooled wall
until it has solidified sufficiently to be form-stable. After the necessary cooling
period the mould is opened and the component removed.
Blow moulding is strictly only suitable for manufacturing closed, hollow
I r - -- - - -- - - n ip ro lls
gantry
to haul -off unit
vertical die --~~-----"'" extruder
air
Figure 1.6 Bl own fi lm - tubula r process
mould open
t
air
parison fed over mould closed air inlet to
bottom mandrel blow bottle
Figure 1.7 Blow moulding
INTRODUCTION 15
objects, such as containers, although many complex shapes can be produced
by ingenious adaptations of the technique. Machines and moulds are
expensive, although less so than injection moulds, but fast production of small
components to 1.5 m 3 capacity containers is possible.
(vi) Injection blow moulding. In an analogous process, injection moulded

preforms are reheated, and the secondary shaping achieved by blow moulding;
this process is also the basis for the manufacture of stretch-blown bottles, in
which balanced orientation is imparted to the wails of the bottle by extending
the preform longitudinally, then blowing it radially. Bottles based on PETP
and PVC made by this method dominate the market.
(vii) Thermoforming. This is a secondary shaping process which uses sheet

or foil as feedstock, and forms a component by heating, followed by shaping,
often using vacuum or compressed air. The sheet is first heated in an air oven,
or more usually, by infrared heaters; single-sided heating suffices for sheet up
to 3 mm thickness, otherwise double-sided heating is employed. When the
sheet has softened, the component is shaped using a male or female mould,
with a plug frequently involved to assist drawing (Figure 1.8). In the female
mould, vacuum is applied to draw the material into the cavity (Figure 1.8a). If
the draw is deep, much thinning will occur at the corners; however, this may be
remedied if a plug is used to stretch the material before the vacuum is applied
(Figure 1.8b). Alternatively, a male mould can be used on deep drawn sections,
especially if compressed air is used to expand the sheet initially (Figure 1.8c).
The mould can then be brought into contact with the stretched sheet, and the
sheet collapsed to take the mould shape.
a c
b
,,
II
,I
vacuum
~2:ZI~:
..,:
II
Iz:z:;l2Zz:2::I
vacuum
compressed ~vacuum
air
Figure 1.8 Thermoforming

1.5.2 Processing methods for cross-linking plastics

These methods involve the reactive processing of a prepolymer (or oligomer),
or occasionally monomers, with a catalyst or a curing agent, as part of the
shaping operation.
(i) High-pressure moulding. Important methods include the following

techniques.
Injection moulding of thermosetting plastics, sometimes known as direct
screw transfer, is very similar to the injection moulding of thermoplastics
except that the plasticization is achieved at low temperature (60- 90°C), and
the curing occurs in the mould, which is at a temperature that produces rapid
cross-linking (140- 200°C). The material remains in the mould until it is cured
sufficiently to be stable in shape (i.e. has green strength), when it can be
demoulded although still hot. Injection moulding is used increasingly,
particularly in respect of the high degree of automation possible in the process.
Typically phenol-formaldehyde novolaks and amino-plasts are processed this
way. A variant is the shaping of dough moulding compounds (DMC), based on
catalysed and glass-filled polyester materials.
Compression moulding is carried out on moulding powders or sheet
moulding compounds (SMC). The presses are vertical, with the hydraulic
cylinder above or below the horizontal platens. The mould is heated to
between 160 to 200°C, being thermally insulated from the platens (Figure 1.9).
The required amount of prepolymer (mixed with catalyst or curing agent) is
placed into the open mould; it is then closed and pressure is applied to cause the
material to flow around the cavity. The mould remains closed until the
mould open mou ld closed
thermal insu lating plate top half
preform of
required mass
of materia l
thermal insulating plate bottom half

of mould
Figure 1.9 omprcs ion mould ing
INTRODUCTION 17
prepolymer has cross-linked. The non-homogeneity of the polymer melt
during shaping can lead to problems in the finished product, e.g. poor fusion or
dislodged inserts. For sheet materials, the charge is cut and placed in the
mould cavity and pressure is applied to the hot mould to force the material to
take up the shape ofthe cavity. Pressure is maintained until curing is complete.
Transfer moulding is a variant on compression moulding, in which there
is a reservoir of catalysed molten resin, an aliquot of which is 'transferred' to
the mould cavity at an appropriate point in the cycle, in a fairly homogeneous
state.
(ii) Low-pressure moulding. Methods have been developed particularly for

glass-reinforced polyester (GRP) systems. However, they are generally
applicable to most reactive dual component systems, in which liquid
prepolymers can be easily mixed and dispensed into moulds, wetting out fibre
reinforcement, processing being carried out at room temperature. In the
simplest case an open mould is employed, made from timber, aluminium or
GRP itself (polyester or epoxide-based), and having a smooth surface finish.
To this is applied, in sequence, mould release agent; gel coat (free of glass fibre);
glass tissue impregnated with resin (optional); resin with major reinforcement,
repeated to build up the required thickness (hence eventual required product
strength); tissue impregnated with resin (optional); and the final gel coat.
Catalyst (the reaction initiator) is mixed with the resin prior to application so
that it cross-links under ambient temperature conditions, although the
reactivity can be readily adjusted to allow adequate working time before
gelling. Two major processes have been developed: hand lay-up and spray
methods.
In the hand lay-up process, the reinforcing 'mat' is cut to shape and disposed
in the mould manually prior to impregnation with catalysed resin, applied
with brush and squeeze-roller. In the spray process, chopped glass fibres are
incorporated in a spray of catalysed resin applied to the mould. Both
techniques allow the manufacture oflarge continuous mouldings limited only
by the size of the mould.
A variant oflow-pressure moulding is catalysed resin injection into matched
moulds in which the reinforcement has been preplaced prior to mould closure;
vacuum applied before resin injection assists mould filling. All these techni-
ques depend on the easy flow of the prepolymer and good wetting of the
reinforcement, but preclude the addition of much cheap particulate filler.
(iii) Dual component dispensing techniques. Many thermosetting plastics,

(e.g. polyurethanes, epoxides, silicones, modified polyesters, phenol-
formaldehyde and amino-plasts), and some thermoplastics (e.g. modified PA 6
and certain acrylics), can be shaped directly from two (or more) low-viscosity
liquid monomeric components, which have to be mixed in precise stoich-
iometric proportions immediately before processing. Several dual component
ISOCYANATE POLYOL >--'
MAC HINE T"NK M"CHINE TANK 00
a (.J"CKETEO) (.JACKETED "NO STIRRED)
REC I RCULA T I ON REC I RCLLAT I ON
I
,,
I
" MIX -HE!r.O I
, / "d
--- - - - - ... - r<
---- - -- >
[/J
~~~ _':'~~~~~':~ _~~<:':l~~ ~ <:~~'_1:"!Ji:-':l~~D HIGH ?RESSURE IMPI NGEMEN T M ~ ~ - HE"D ::l
()
--- - ~ ----- --- ----------- - --,--- == ::I ~ =====================::: ~ , =:== [/J
sOLVENT ~LUSH " I ,
I~ RECIRCLl..AT ION D I SPENSe:',

I AIR ~Ll ' ~
RECI/'1~LAT ION I u REC lr~~TION ,I f\SSS?5J ():5:):'5J '\
I ~ II n I " \ I
,, ~
:;
I I , r<
[/J
•
•
.......
•
•
I SOC~ ANATE~~
,
I
I
,,
I
, I I
I
" .... NOZZLE WALL OF Mou...O
STIRRER
"
b c ------_ ...
Figure 1.10 (a) Schematic diagram of dual component dispensing equipment. (b) Low-pressure
mechanical mix-head. (c) High-pressure impingement (or contra-flow) self-cleaning mix-head
INTRODUCTION 19
dispense methods with accurate metering of ingredient outputs, and sub-
sequent ratioing and mixing of ingredient streams, have been developed (see
Figure 1.10).
Polyurethanes are the best example of materials using low-pressure
dispensing. Here a polyol blended with catalyst, blowing agents, etc., is held
conditioned in a tank, and the isocyanate in a second tank. An ingredient is
pulled from its tank and metered using a constant volumetric displacement
pump, which when combined with restrictions in-line develops pressure and
velocity in that ingredient stream. By adjusting the output on each pump, both
a stoichiometric ratio and output rate (a shot) can be established. Gear pumps
will develop only a few bars pressure, enough to feed a mix-head. To produce
polymer, both streams are allowed to enter the mix-head, in which a
mechanical propeller rotating at 5000-15000 rpm shears and intimately
mixes the ingredients, which will then rapidly exit through the head's nozzle
(Figure 1.10a). The low velocity with which the ingredients leave the head
allows pouring without splashing. Once a shot is fired, three-way valves shut
ingredients offfrom the mix-head, and residual ingredients must be flushed out
using a suitable solvent followed by an air blast; this leads to waste problems.
The low-pressure equipment is used for open- and closed-pour moulding and
the manufacture of foam slab-stock.
High-pressure dispensing is achieved using any of a variety of piston pumps
(e.g. radial type), where pressures of 150-250 bars are developed (lower for
polyamide reactants). A typical high-pressure mix-head consists of cylinder
with inlet and return ports, and a hydraulically operated ram (Figure 1.10b).
On recirculation, each ingredient stream from the pump passes along a small
groove in the side of the ram, and back to its tank. When a shot is fired, the ram
retracts, clearing the inlet ports but sealing the return ports. High pressure,
combined with small cross-sectional area at the inlet port, means that each
stream will enter the mixing chamber with high velocity and kinetic energy.
The energy will be mostly converted into complete and intimate impingement
mixing of the two streams: each stream needs to reach a minimum critical
Reynolds number for good mixing-lOO or more for cellular products, and
150 or more for non-cellular products. The residence time in the mix chamber
is very short and the mixed ingredients will rapidly leave the head's nozzle at
1-2 m s -1. Normally, ingredients can only be safely injected into a mould
cavity. The high-pressure equipment is used predominantly in reaction
injection moulding (RIM) processes, although modification of the mix-head
permits spray processing, and open- and closed-pouring. The viscosity of the
ingredients should not be above 5 Pa s for successful pumping and mixing,
although heating ingredients can be an effective way of reducing viscosity.
Fibre and particulate filled systems can only be processed on modified high-
pressure equipment. Since low-viscosity mixed ingredients are injected into
the mould cavity, filling is achieved with relative ease, the maximum pressure
in the mould being 3 bars for some foamed systems, and less than 1 bar for most
other systems (compare to approximately 1500 bars for injection moulding

thermoplastics). As a result, cheaper weaker tooling materials (e.g. aluminium
and kirksite alloys, reinforced epoxide resin), along with smaller clamping
presses can be employed; toggle or G-clamps will even suffice with smaller
moulds. Equally, maximum moulding weight possible with RIM equipment
can exceed 100 kg, with clamping forces required to hold the mould closed
being less than a tenth of those needed for thermoplastic injection moulding.
However, steel tools have to be used in long production runs.
1.6 Interactions between shaping process and plastics materials

There are two events in the shaping process which would be expected to
influence the properties of the product via their effect on the materials being
processed. These are movement of material to accomplish shaping, and change
of phase to achieve stabilization of shape. There may be additional interac-
tions, such as if homogenization is not achieved prior to shaping, or when
additional material is packed into a mould to compensate, in part, for
shrinkage. However, most problems in practice arise either from failing to
conform to the principles already discussed in this chapter, or from failure to
appreciate the significance of the two factors given above.
A consequence of the movement of polymer during shaping is a tendency of
the polymer chains to orient in the direction of flow. Further, if anisotropic
fillers are incorporated in the formulation, these will also be influenced by the
flow geometry. These phenomena are inevitable and can only be reduced to
acceptable levels by attention to the detail of the shaping process, or by
harnessing orientation to reinforce the component in the direction of
maximum stress by appropriate mould or part design. Orientation, and
consequently anisotropy of mechanical properties, is frozen into the compo-
nent by the shape stabilization stage. Orientation generally leads to birefring-
ence, the occurrence of different refractive indices in the material for different
directions of viewing. At the factory-floor level, this can be a useful effect since,
in its simplest form, it can be seen by placing a transparent moulding between
crossed Polaroid TM sheets. For translucent and opaque objects the
procedures are a little more complicated.
The stabilization stage, necessarily involving a phase change from liquid to
solid, has several consequences.
(i) Shrinkage. Thermoplastics have higher specific volumes in the melt than
in the solid state. This is true for amorphous thermoplastics and even more so
for crystallizing materials, but some compensation may be obtained by
packing the mould under high pressure, thus taking advantage of the limited
compressibility of the plastics melt. It is sometimes possible to provide more
plastics melt to compensate for the shrinkage, as for example in specially
designed cooling dies for extrudates of thick section or by hot runners in
INTRODUCTION 21
Injection moulding. These palliatives are not effective for cross-linking
(thermosetting) plastics, where the major shrinkage results from the poly-
merization reaction. Shrinkage can be reduced by inert fillers and by shrink
control additives: these are additives, frequently polymeric, which are soluble
in the uncured resin but insoluble in the cured, cross-linked plastic. The
precipitation ofthe additive results in an increase in volume, compared to that
of the solution. The contribution of shrinkage to tolerances is considered in
greater detail in Chapter 2.
(ii) Crystallinity. The crystallinity level attained on cooling a plastics melt

depends on many process and materials factors. A very important factor is the
rate of cooling, rapid chilling leading to lower levels of crystallinity with
consequent decrease in mechanical strength, modulus and (usually) an
improvement in toughness.
(iii) Crystalline texture. Cooling of a plastics melt can only be accomplished

by heat transfer by conduction to a heat sink. On simple heat-transfer grounds
alone, therefore, cooling times can be minimized by using moulds or cooling
baths, as cold as practicable. This frequently leads to a quenched zone of
reduced crystallinity and finer crystalline texture which hitherto has been
assumed to be beneficial to mechanical properties. However, there is mounting
evidence that some mechanical weakness resides in the boundary between this
region of fine texture and the bulk of coarser crystalline material. The use of
cold moulds in injection moulding of thermoplastics may restrict flow unduly,
leading to short mouldings or to unacceptable levels of residual strain.
Further reading
Polymer science
Bassett, D.C., Principles of Polymer Morphology, Cambridge University Press (1981).
Billmeyer, F.W., Textbook of Polymer Science (3rd edn.), Wiley-Interscience, New York (1984).
Cowie, 1. M.G., Polymers: Chemistry and Physics ofModem Materials, International Textbook Co.
[Blackie Publishing Group], Glasgow and London (1973).
Haslam 1., Willis, H.A. and Squirrell, D.C.M., Identification and Analysis of Plastics (2nd edn.),
IlifTe [Butterworth], London (1972).
Parker, D.B.V., Polymer Chemistry, Elsevier-Applied Science, Amsterdam (1974).
Rodriques, F., Principles of Polymer Systems (2nd edn.), McGraw-Hill, New York (1982).
Plastics properties
Brown, R.P., Handbook of Plastics Test Methods, Godwin [Longman Group], London (I98\).
Brydson, 1.A., Plastics Materials, IlifTe [Butterworth], London (1982).
Blythe, A.R., Electrical Properties of Polymers, Cambridge University Press (1979).
BS 4618, Recommendations for the Presentation of Design Plastics Design Data. British
Standards Institution, London.
Crawford, R.J., Plastics Engineering, Pergamon Press, Oxford (1987).
Hall, c., Polymer Materials: An Introductionfor Technologists and Scientists, Macmillan, London
(198\).
Heade, lW.S., Polymers and their Properties: Vo!.l: Fundamentals oj Structure and Mechanics,
Ellis Horwood, Chichester (1982).
Ogorkiewicz, R.M., Thermoplastics: Properties and Design, Wiley-Interscience, New York (1974).
Ogorkiewicz, R.M., The Engineering Properties oj Polymers (Engineering Design Guides
No. 17), Oxford University Press (1977).
Turner, S., Mechanical Testing oj Plastics (2nd edn.), Iliffe [Butterworth], London (1983).
Polymer manuJacturing and processing

Becker, W.E., Reaction Injection Moulding, Van Nostrand Reinhold, New York (1979).
Brown, R.L.E., Design and ManuJacture oj Plastic Parts, Wiley-Interscience, New York (1980).
Brydson, lR., Flow Properties oj Polymer Melts (2nd edn.), Godwin [Longman Group] (1981).
Cogswell, F.N., Polymer Melt Rheology, Godwin [Longman Group] (1981).
Fenner, R.T., Principles oj Polymer Processing, Macmillan, London (1979).
Radian Corporation, Polymer ManuJacturing: Technology and Health Effect, Noyes Data
Corporation, Park Ridge (1986).
Tadmor, Z. and Gogos, e.G., Principles oj Polymer Processing, Wiley-Interscience, New York
(1979).
2 Fundamentals of design
Design is an exercise embracing many considerations: mechanical perfor-

mance and cost are obviously relevant, and the latter has many constituent
elements, of which mass cost (or more appropriately, volume cost) is one of the
most important. Data are given in Table 2.1; however, manufacturing cost can
modify the overall cost very considerably, and as the cost of plastics is very
unstable at present, data in Table 2.1 must be regarded as only approximate.
Different shaping methods are employed for plastics and each has an
associated processing cost depending mainly on the production quantity
required. For instance, the initial capital cost of equipment for injection
moulding and extrusion can be very high, whereas the cost for equipment in
GRP hand lay-up may be merely the cost of a wooden former. Expensive
processes can only be justified if the production quantity is large, allowing the
costs to be absorbed, thus making the processing cost per item acceptable.
2.1 Engineering design

When a component is subjected to an external load, stresses are created within
the component and it will deform or deflect. In metals and other materials, the
stresses and deflections can be calculated because the material behaves linearly
(in the elastic region) when an external load is applied (Figure 2.1). This,
commonly known as Hookean or linear elasticity, can be used for many design
applications for metals because the deformation is proportional to the load for
a constant cross-section area. When most plastics are subjected to a similar
situation, the relationship is non-linear (Figure 2.2). This response to applied
force is generally described as viscoelastic because the material behaves partly
as a fluid of very high viscosity and partly as an elastic solid. The traditional
engineering relationships used by the designer based on Hookean principles
are inadequate, but if the plastic is assumed to behave linearly, the designer can
calculate the stresses and deflections for short-term loads.
If the load is maintained for a long period the material will continue to flow
as a high-viscosity fluid (Figure 2.2). This introduces the important concept of
'creep' into plastics design. The amount of creep will depend on the
temperature of the component under load, the length of time the load is
applied, and the stress level (Figures 2.3, 2.4). This same information can be
presented in various other ways; either by a stress vs. strain graph with curves
Table 2.1 Usage and mass cost of plastics materials
Usage (Tonnes x 1000)

Plastics materials 1984 1985 1986 Price Band'
Thermoplastics
Low density polyethylene (LDPE)j 510 580 610 A
Linear low density
polyethylene (LLDPE) A/B (C B copolymer)
High density polyethylene (HDPE) 210 250 275 A
Polypropylene (PP) 297 330 370 A (homopolymer)
B (copolymer)
Orientated polypropylene
(OPP) film 39 40 43 G
Poly(vinyl chloride)(PVC) 444 450 484 A
B (emulsion)
Polystyrene (PS)/styrenics 146 148 156 B (crystal)
B (HIPS')
Expanded polystyrene (XPS) 31 29.5 33 C
Acrylonitrile-butadiene-styrene (ABS) 53 55 58 E
Polyamide (PA) 20 22 23 G (PA 6 and 6.6)
I (PA 11 and 12)
Poly(oxymethylene) (POM) 10 10.8 12 D/E
Thermoplastics polyesters 37 41 45 D/E (PETp 2 )
G (PBTp 3 )
PETP film 23 23.7 24.4 G
Poly(tetralluoroethylene) (PTFE) 1.25 1.35 1.4 I
Poly(methyl methacrylate) (PMMA) 27 28 29 F
Poly(phenylene oxide)/
Polystyrene (PPO/PS) 6.0 5.8 G
Thermosets
Phenol-formaldehyde (PF) resins 49 50 49 D-F (Novolak resins)
B (Resol solution)
D/E (Resol-100% solids)
PF (moulding grades) 14 14 12 B
Amino-plasts 122 125 131 C/D (UF 4 moulding powders)
C/D (MF 5 moulding powders)
A-D (MF impregnation
resins and solution)
Unsaturated polyester resins (UPR) 50 51 53 E/F
Epoxides* 17 17.5 18.5 F
Polyurethanes* (PU) 91 94 100 D/E (foams)
E-G (elastomers/resins)
G (thermoplastics grades)
Notes
t Price band is based on the average cost of tonne lots for the UK in 1987.
A £400-£600 F £1500-£2000
B £600-£800 G £2000-3000
C £800-£1000 H £3000-£5000
D £1000-1250 I> £5000
E £1250-£1500
Abbreviations
(1) HIPS High impact polystyrene,
(2) PETP Poly(ethylene terephthalate),
(3) PBTP Poly(butylene terephthalate),
(4) UF Urea-formaldehyde,
(5) MF Melamine-formaldehyde.
*Epoxide and polyurethane materials are available in many chemical forms. Prices in-
dicated based on the general-purpose, rather than specialist grades.
FUNDAMENTALS OF DESIGN 25
u c:
'';:; 0
rn .-
III Cl
- Q)
Q) ~
mild steel
plastic
assumed linear performance
strain
Figure 2.1 Typical stress vs. strain curves for metal and plastic
constant load
~ 3
2
c:
.~
rn
o~~--~------------~_
0·1 100 104
time (hours)
Figure 2.2 Schematic representation of a creep curve
O
0. o. ;1:iSOCh~:nousstres::s strain
; ;
isometric stress
_ _ _ _ _ _ __ ~I _ _ _ _ v~. ~og time
3 ~
c:
.~
2
ti
0~0~·1~--~--~1~0--------1-0~0-0--
time (hours)
Figure 2.3 Creep curves at 20°C for various stress levels
T,
O~O~·O-1------~-----1~O~O~----1~O~4-
time (hours)
Figure 2.4 Creep at various temperatures
1 hr
100 hr
104 hr
o 2 3 4 5 6 7
strain (%)
Figure 2.5 Isochronous stress vs. strain curves derived from creep data
30
l
~
20
-----_..=:t:::!E= 2%
I E= 1%
O~~------~----~~----~I~~
0·01 100 104
log time (hr)
Figure 2.6 Isometric stress vs. log time curves derived from creep data
~lIed polyamide 6.6
~OlyetherSUIPhone
~-=u=nplasticized PVC
0·01 100 1 yr
time (hr)
Figure 2.7 Long-term strength data for some thermoplastics
at different times (Figure 2.5: this is an isochronous stress vs. strain curve) or by
a stress vs. log time curve to show the maximum design stress (Figure 2.6: an
isometric stress vs.log time curve). Both curves can be derived from the creep
data at 20o e, as indicated in Figure 2.3.
The maximum strength will vary with time (Figure 2.7) and temperature. A
designer, faced with the problem of designing a component, can use a criterion
either of maximum stress or of maximum deflection. Strain-limited design is
adopted for ductile plastics, whereas strength is used as the basis for design
with brittle materials and for brittle failure in otherwise ductile materials. For
example, if a tie bar made from propylene homopolymer were to be
continuously loaded at 20 e for one year, what would be the design stress for
0
the tie bar? The designer could use a design criterion of maximum long-term
strength of 18 MPa (Figure 2.7) and apply a safety factor of 1.5, to arrive at a
design stress of 12 MPa. The value of the safety factor will depend on a number
of variables (such as shape, position of load, stress concentrations, weld or
joins), so for a simple bar a safety factor of 1.5 can be assumed to be adequate.
However, from creep data, after one year at a stress of 12 MPa, the bar will
have extended more than 4% of its original length. This will lead to stress-
whitening, which is unattractive, but additionally a strain of greater than 4%
may be unacceptable as well as giving the appearance of weakness. The part
could be designed with a maximum strain criterion of 3%; then the design
stress of9 MPa can be obtained directly from the isometric stress vs. time curve
Table 2.2 Upper strain limits (%) for representative

plastics
Glass Reinforced Polyamide 6. 6 1.0

Acetal copolymer 2.0
Polypropylene 3.0
Polypropylene with welded joints 1.0
ABS 1.5
Polyethersulphone 2.5
c:
.~
ti
'1:J
Q)
0·9
i»
>
0
0
~
0·8
to
c:
.,.
.0 0·7
0
~ 0·6
10- 2 10-' 10° 10' 10 2
reduced time
Figure 2.8 Fractional recovered strain vs. reduced time (PBT at 20°C)
(Figure 2.6). Although this value is lower than the previous design stress
derived from maximum strength, it is likely to produce a more acceptable
product.
The maximum strain criterion is becoming popular for plastics materials
subjected to long-term loads; upper strain limits for representative plastics are
suggested in Table 2.2. Thus the appropriate design stress at a particular
time and temperature can be found in the relevant creep data.
When a load is removed from a metal part, the recovery from strain, if it
occurs, is instantaneous. With plastics, much of the strain is recovered
reasonably quickly but a proportion is recovered only after a period of time.
Thus, recovery, like creep, is time-dependent. Recovery data are provided as
fractional recovered strain vs. reduced time (Figure 2.8), where:
. . Strain recovered
FractIonal recovered stram = T I . hId . d
ota creep stram w en oa IS remove
and
·
Red uce d tIme Recovery time
= ~--.--~---
DuratIOn of creep period
The effect of intermittent loading on creep properties is less than for
continuously-loaded applications, but intermittent loading may introduce
fatigue; the resistance to fatigue varies between materials. Examples of
intermittent loading are shown in Figure 2.9 for different stresses and loading
and unloading periods.
Impact strength is often a very important design requirement and is affected
by three principal factors-temperature, stress concentration and materials
factors. It is important to remember that a tough material may behave in a
brittle manner at low temperature; however, stress concentrations are the
most common source of failures in practice because of the very high stresses
induced at corners, holes, keyways, etc .. An example of the effect of stress
continuous 15 M Pa
-- ....... intermittent (1 :5) 10 MPa
=::-- --- ---

.... - intermittent (1 :11) 10MPa
0·01 0·1 10 102 10 3 104

total creep time (h)
Figure 2.9 Creep under conditions of intermittent loading (propylene copolymer at 20°C)
2 mm notch tip radius
E
.......
3
.t:
C,
c:
~ 100
'iii
ti 0·25 mm notch tip radius
'"Co
.§
0
-80 -40 0 40 80
temperature (,C)
Figure 210 Impact strength vs. temperature (rigid PVC)
.t:
parallel to orientation
j<----- transverse to orientation
degree of orientation
Figure 2.11 Effect of orientation on tensile strength of polystyrene injection mouldings
Table 2.3 The impact strength of thermoplastics (ICI Technical Service Note G 123)
Temperature (0C)
Material -20 -10 0 +10 +20 +30 +40 +50
Polystyrene A A A A A A A A
Acrylic A A A A A A A A
Glass-filled polyamide 6.6 A A A A A A A B
(dry)
Poly(4-methylpentene) A A A A A A A AB
Polypropylene A A A A B B B B
Poly(methyl methacrylate)
(craze-resistant) A A A A B B B B
Poly(ethylene terephthalate) B B B B B B B B
Polyacetal B B B B B B C C
Rigid PVC B B C C C C D D
CAB B B B C C C C C
Polyamide 6.6 (dry) C C C C C C C C
Polysulphone C C C C C C C C
High-density polyethylene C C C C C C C C
Poly(phenylene oxide) C C C C C CD D D
Propylene-ethylene
copolymers B B B C D D D D
ABS B D D CD CD CD CD D
Polycarbonate C C C C D D D D
Polyamide 6.6 (wet) C C C D D D D D
PTFE BC D D D D D D D
Low-density polyethylene D D D D D D D D
Notes
A. Brittle: specimens break even when unnotched
B. Notch brittle: specimens brittle when bluntly notched but do not break when unnotched.
C. Notch brittle: specimens brittle when sharply notched.
D. Tough: specimens do not break even when sharply notched.
concentrations is shown in Figure 2.10. It is the designer's concern to radius

corners and avoid stress concentrators in an area susceptible to impact or
other loads. The effect of orientation is to introduce anisotropic properties to
the component which will reduce the impact strength (Figure 2.11).
A list of plastics materials in order, from the most brittle to the most ductile
is given in Table 2.3. However, it is important to appreciate that toughness in
impact does not imply good fatigue behaviour.
2.1.1 Fracture mechanics applied to plastics

Sometimes plastics products, such as toys and domestic commodities, fail
prematurely. This may be caused by poor materials choice, bad processing,
poor-quality material, poor design, or for other reasons. In items such as pipe
and storage vessels, failure can be catastrophic, and designers seek to produce
safer products. Fracture mechanics aims to assist the designer in understand-
ing the mechanics of crack growth by answering the following questions:
F
Figure 2.12 A crack subjected to opening forces
(i) What will be the residual strength of a cracked part with a change in crack
size?
(ii) What is the critical crack size for catastrophic failure at the expected
service load?
(iii) How long will it take to grow a minor crack to a critical crack size?
Most of the theory developed to date has been concerned with the behaviour
of cracks or crack-like defects produced by opening forces (Figures 2.12, 2.13)
applied to linear elastic brittle materials. More complex analyses have been
developed for cracks induced by shearing or tearing, but these are beyond the
scope of this text. On first consideration, the relevance of a fracture mechanics
approach to plastics which are predominantly ductile may be questioned, but
further reflection confirms that most unexpected failures are brittle in nature.
For tensile stress fields, the basis of the fracture mechanics calculation is the
way the stress is concentrated in the region of the crack or defect, described by
the stress intensity factor, K,. Consider a thin plate of infinite size (Figure
2. 13 a), containing a through-thickness crack of length 2a, subjected to a
uniform uniaxial stress, (J, measured remote from the crack (the stress is
normal to the crack growth). The stress is enhanced near the crack tip (stress
Figure 2.13 Further analysis of a crack subjected to opening forces

concentration), this local stress, (Jy (see Figure 2.l3b), being given by
(Jy = K([2nrr/2
where r is the distance from the crack tip along the direction of crack growth,
and
K( = (J [naJ 1/2( = linear elastic stress intensity factor)
These equations show that the local stress is proportional to the applied stress
and varies with the square root of the crack size. K( is independent of the
material from which the plate is made, provided that it is linear elastic. K( does
depend on the size and location of the flaw (and on the applied stress). The
location of the crack in relation to the plate geometry is incorporated in a
modifying factor, Y.
K( = y.(J. [nar/ 2
Values of Y can be obtained from appropriate texts [ll

The considerations so far have not taken account of the properties of the
material under stress, the only requirement being that it is linear elastic. The
material will fail by very rapid crack growth when K( reaches a critical value
for the material K(c> often called the fracture toughness. Typical values for
fracture toughness for different plastics subjected to short-term loading are
given in Table 2.4.
The relationship between applied stress and critical crack length for
catastrophic failure under an opening force is shown in Figure 2.14 for a range
of values of fracture toughness: the importance of this parameter is clearly
seen. Fracture toughness is affected by factors which affect strength, including
time under load, temperature, nature of the environment, effect of processing
conditions and molecular weight. Thus deciding whether a product is likely to
fail depends on the relevant value of the fracture toughness, the applied stress,
the flaw size and the dimensions of the article, together with the nature and
location of the crack, as expressed by Y.
However, it is not possible for the applied stress to exceed the failure stress,
(JF' for the material. If (JF is applied to the product which does not contain a
Table 2.4 Typical values of fracture toughness at 20°C in air.
Material
Epoxide 0.6
Polystyrene 1.0
Poly(methyl methacrylate) (cast sheet) 1.6
Polycarbonate 2.2
PVC (pipe compound) 2.3
High-density polyethylene 3.0
Polyamide 6.6 3.6
60
co
a..
50
:2
-; 40
~
1ii 30
]
~
<II
20
10 3·0
1.5 2·0
o
0·1 10 100
crack length (2a mm)
Figure 2.14 Relationship between applied stress and critical crack length for catastrophic failure
for various values of fracture toughness
deliberately introduced flaw, then it is possible to calculate the inherent flaw

size a IFS that the material seems to have:
aIFS = Klc' [no} y2] - 1
It would seem that if there were a crack in a structure there would be no reason
to be concerned, provided its size was smaller than the critical crack size. This
is not true-any crack in a body under stress will gradually increase in size with
increasing speed, until catastrophic failure occurs when KI = K 1C' The crack
growth rate, a, is given by:
a:::eCK~
for materials under constant tensile stress, with C and n constants, depending
on the materials and test conditions. Experiments have shown that there are
frequently three distinct areas of crack growth: slow crack growth (smooth
fracture surface) followed by intermediate growth and finally fast growth
(rough fracture surface). For each region, different values of C and n apply.
The time taken for a crack to grow can be found by integrating the crack
growth equation between the original size of the crack and the new size of the
crack.
2.2 Design limitations imposed by processing method

Before product design can commence in earnest, the designer must have
considered which processing method to employ, since this has a direct bearing
on the design.
GRP hand lay-up methods are suitable for simple open design shapes (chair
shells, covers, etc.) which can be easily removed from the wooden or metal
former; otherwise, more complex large enclosed shapes (such as truck cabs)
can be manufactured if the former can be dismantled after moulding.
Generous tapers of 2° or more are necessary to assist removal from the mould.
Localized highly stressed areas can be made thicker and stronger by
appropriate placement of the reinforcement.
Rotational moulded parts (dustbins, barrels, etc.) are usually enclosed
sections. Generous radii are necessary to assist flow into corners; sharp corners
would make the section thin, as well as acting as stress concentrators, making
them very weak. Normally the bulk powder volume should be no more than
50% of the cavity volume, otherwise bridging from one side to another will
occur. Ribs, lugs, surface features and textured surfaces are possible for
rotationally moulded parts. Mouldings produced by rotational casting have
very little residual orientation, and the long cooling time will tend to produce
highly crystalline mouldings.
Sheet thermoformed parts (vacuum forming) are usually simple in shape
and have all the features in two dimensions (baths, small boat hulls, body
panels, dispenser cups, etc.). The main criterion for thermoformed parts is the
length of draw to the original sheet thickness, because this will directly affect
wall thickness. Thinning will occur at the corners, so generous radii are
necessary to reduce the inherent weakness at these points. Corrugations can be
used to increase the stiffness of the part perpendicular to the corrugations.
Orientation is induced in the direction of draw, and remains in the finished
moulding. Reproduction of mould image is limited, e.g. sharp corners
becoming rounded, since thermoforming does not involve a plastics melt;
reproduction becomes worse through the thickness of the moulding.
Blow moulding is used to manufacture enclosed shapes (bottles, barrels,
containers, etc.) where the shape is simple. Screw threads can be formed on the
top, corrugated sections can be used to stiffen the product, and handles can be
incorporated. Thinning will occur on the corners of the base and also on the
corners in the sides of square bottles, but can be reduced by blowing a profiled
parison. Some orientation is created in the blowing the parison, and is largely
retained in the finished product (e.g. at a maximum in the vertical walls of a
bottle).
Extruded parts are normally one-dimensional and of a simple cross-
sectional shape (curtain rail, rainwater gutters, pipe, or films which are
produced from a very wide die and hauled off at a faster rate to produce
orientation). In the extrusion of sections, the part thickness will affect
distortion, and may lead to sinking and voiding. The polymer chains are
extended in the direction of extrusion and the properties are correspondingly
anisotropic.
Thermoplastic injection moulding is by far the most common moulding
process in use, as well as being amongst the most complex. Normally, injection
moulded parts have features which are formed parallel to mould opening (two-
dimensional features). Features perpendicular to mould opening are possible
but these are formed using complicated tooling arrangements. This manu-
facturing method is suitable for complex parts provided they are not fully
enclosed.
Reaction injection moulding involves an additional factor in process
control, that of shaping of reacting monomers, which have to be dispensed in
controlled stoichiometry to ensure complete polymerization and cross-
linking. With the exception of fibre-filled materials, orientation is limited in
RIM products.
2.3 Product design

Mention has been made previously of the two different classes of plastics
materials-thermoplastics and thermosetting plastics-and to additives affect-
ing mechanical properties (fillers, glass reinforcement, blowing agents). Each
of these subgroups has different design principles and the additives alter the
way in which the component 'Should be designed.
2.3.1 Thermoplastics
Thermoplastic injection moulding of constant thin cross-sectional thickness is
necessary to avoid surface sink marks and voids within the core (Figure 2.I5a).
This will also assist in reducing distortion and result in more accurate
tolerances for a part. The wall thickness of ribs and bosses must be kept to less
than 2/3 of the main wall thickness to prevent sink marks appearing on the
surface (Figure 2.I5b).lfthick ribs are necessary, it may be possible to disguise
the sink marks by surface features (Figure 2.I5c, d). Flat plates are susceptible
to warping; additional ribbing or corrugating the surface will produce a much
more rigid structure (Figure 2.I5e).
The melt in a mould cavity will be forced to flow around holes and slots,
joining again after the hole to form a 'knit line' or 'weld line'. The gates should
be positioned so as to reduce the number of weld lines to a minimum, because
weld lines are potential weak points in any moulding. Similarly, in extrusion,
the melt is sometimes forced to flow around restrictions in the die, and weld
lines are formed, which again can create a weakness in the product.
Thermoformed and blow moulded parts have flat sections or straight sides
which are susceptible to warping and bending. It is again possible to reinforce
these sections by using a corrugated shape.
2.3.2 Thermosetting plastics

These materials are shaped by reaction processing, such as screw transfer
injection or compression moulding, although glass reinforced polymers (GRP)
are frequently moulded using hand lay-up or spray techniques. The injection
techniques and compression moulding of cross-linking plastics do not have
poor design good design

thin cross-section to avoid
sin~
k . ng
..-: - sinking and voiding
(a) .... -'1 voiding
sink mark : \ -.it

(b) ~f
--J li!
t= main wall thickness
good design practice
~
(d)
(0)
sink mark is camouflaged sink mark is camouflaged

bya bead
by a change in section
(')L J
ribbing to prevent warping
Figure 2.15 Common moulding faults and some corrective measures
the same limitations as thermoplastics injection moulding regarding wall

thickness, rib size, etc. In part, this is due to the very low viscosity of melts or
mixed monomers when flowing around the mould cavity, compared to that of
thermoplastic melts. Mouldings with thick sections and with varying sections
do not create any problems except that cure time may be affected by thickness.
A generous draft angle (approximately 2°) is necessary to assist the ejection of
the moulding from the mould.
2.3.3 Foams and reinforced plastics

Occasionally, the attractive properties of polymers fall short of the needs of a
designer. One way of altering these is to include an additive to improve
properties to those required. Blowing agents and reinforcing fillers will change
the basic properties of a polymer: as well as the mechanical properties, the melt
flow properties are changed, and this may affect flow length, mould filling and
mould cycle times as well as the mechanical properties indirectly, for example
by increasing anisotropy.
(i) Foams. The manufacture of foamed parts had been restricted to the
cheaper polymers and polyurethanes, although the range now includes
engineering thermoplastics. Foams are often classified by density: low-density
foams (10-100 kg m - 3) are used in packaging, cushioning materials and
thermal insulation; medium-density foams (100-600 kg m - 3) are used for
footwear, furniture and impact restraint pads; high-density foams (greater
than 600 kg m - 3), sometimes referred to as 'structural' or 'micro cellular'
foams, are used in many 'rigid' applications, for example washing-machine
tubs, television panels, business-machine covers, vehicle panels and artificial
leathers. In general, the advantages of a structural foamed part over an
unfoamed plastics component are:
Cost reduction
Increased rigidity for the same polymer weight
Reduced weight
Possibility of moulding thick and thin sections.
Furthermore, the manufacture of foams is attractive because it is possible to
reduce manufacturing costs. This is possible because the mould has greater
cross-sectional thickness, which reduces the resistance to the flow ofthe melt in
the mould and consequently requires much less injection pressure. Also
resulting from the reduced injection pressure for thermoplastic foams, the
mould clamping force is much less and needs only to keep the two halves of
the mould closed during the foaming stage. Thus, the injection machine
required can be much simpler and consequently cheaper than the traditional
injection moulding equipment. With thermoset foams such as polyurethanes
made by dual component processing, injection pressures are very low, and
mould tools need only resist pressure from the expanding foam. However,
mould orientation and location of filling points are critical, especially in long
and narrow cross-sectional area moulds (e.g. chair shells), to avoid foam
density differentials within the length of the moulding.
Structural foams consist of a low-density cellular core sandwiched between
solid integral skins. Foamed parts are mainly manufactured using either both
types of injection moulding, or an extrusion process with a polymer melt or
liquid monomers containing an inert gas. The inert gas can be generated in a
number of ways, e.g. decomposition of a chemical by heat or water, boiling of a
liquid due to the exotherm from reacting monomers, or by the addition of a
compressed gas (usually nitrogen or fluorocarbon) into the melt before
injection. The solution is injected into a mould cavity and is then allowed to
expand in the cavity. With thermoplastics, a solid skin is formed by the
solidification of the melt before expansion can take place. This skin forms an
insulating layer for the core to expand by foaming. Experience with foams
has shown that the stiffness and strength vary with the square of the foam
density, for densities in the range 400-1 000 kg m - 3.
The advantage of a foam can be demonstrated by considering two
components with the same mass, with the foamed version having the greater
thickness. The bending stiffnesses can be compared for a simple rectangular
beam, for solid polymer (density 1 000 kg m - 3) and foam (density 700 kg m - 3).
Calculation shows that the foamed beam is 43% stiffer than the solid beam
with the same mass. However, this idealized situation is not fully correct
because a moulding will never be homogeneous foam, but will have skins of
solid polymer on the surfaces. This introduces more difficulties into the
analysis of a foamed beam, although equations have been derived to solve the
problem. Typically, polypropylene sections with thicknesses between 6 and 20
mm are recommended, and for design purposes the ratio of skin to core to skin
is 1:4:1 respectively. These rules do not apply so strictly for the semi-flexible
self-skinned polyurethane systems.
(ii) Reinforced plastics. Reinforcement can be obtained by adding fillers,

glass beads or fibres to a basic polymer. Common fillers are clay, chalk, talc
and wood flour which are added to the polymer in quantities up to 60% by
weight. The effect of this addition is to improve rigidity, to reduce moulding
distortion and to reduce costs, but the strength is frequently impaired and the
melt flow length reduced.
Short-fibre composites are most commonly used in parts which are injection
moulded or extruded. Predominantly glass fibres are employed, although
carbon fibres and asbestos are occasionally used. The effectiveness of the
reinforcement relies on the stress in a component being transferred from the
polymer (normally termed the matrix) to the fibre. Thus, a good bond is
necessary between fibre and matrix, and to this end the glass is coated with a
coupling agent which is compatible with the matrix in which it is dispersed.
The mechanical properties of short-fibre composites are difficult to establish
because the properties vary with the quantity of fibres and their orientation.
For example, in a complex injection moulding the glass fibres may not be
equally dispersed throughout the component, with some portions having little
or no reinforcement. The greatest strength of a short-fibre reinforced
component is in the direction of fibre orientation with the least strength
perpendicular to the orientation of the fibre. The analysis of a component
incorporating short fibres is difficult, and the mechanical properties in data
sheets for short-fibre reinforced polymers should be used with considerable
caution. Particular difficulties arise when a designer has to establish the
performance of a component using information provided for uniaxially
oriented test specimens. Great care must be taken in using this information
and, if possible, data for randomly oriented specimens should be employed.
Careful attention must also be paid to the design of a mould, especially the
positioning of gates, in order to provide optimum strength in the critically
stressed areas. Furthermore, the shrinkage in a short glass-fibre-reinforced
moulding is greatest perpendicular to the direction of orientation of the fibres.
This is directly opposite to the shrinkage of unfilled polymers, and a mould
designer must allow for this different shrinkage.
Long-fibre composites are mainly used with hand lay-up systems using
polyester or epoxides as the matrix in which glass fibres are suspended. It is
possible in long-fibre composites to calculate the strength and stiffness more
accurately using conventional composite theory. For example, in a unidirec-
tional continuous fibre composite, the equation for the total stress, (fe' in the
composite can be shown to be:
where V is volume fraction, and the modulus E for the composite is

Ee=EmVm+ECVC
Thus the performance of the composite can be analysed.
2.3.4 Tolerance and dimensional control of products

The successful use of plastics requires an appreciation of the dimensional
accuracy that can be achieved at reasonable cost. Although metal parts only
rarely change after shaping or machining, plastics parts may be subject to
relatively large dimensional changes associated with the following:
(i) Processing scatter: for mouldings, affected by uniformity of moulding
material, machine setting and tool temperature
(ii) Condition of the equipment: for mouldings, manufacturing tolerances on
tool dimensions, tool wear, and positional changes in movable parts of
the tool
(iii) Operating and environmental factors affecting the product.
The dimensional instability of plastics might be regarded as intolerable by
an engineer experienced only in metals behaviour, but the inherent flexibility
and resilience of most plastics materials can be adapted by such design features
as force- or clip-fits.
The shrinkage of thermoplastics which occurs on cooling after moulding
may result in distortion: it is usually defined as the difference in dimensions
between the (moulded) product after cooling and the (cold) metal mould. This
shrinkage is caused by thermal contraction and by the relaxation of moulded-
in stress resulting from orientation of the molecular chains. Thus the shrinkage
of a material will be different perpendicular to the flow than in the direction of
flow, because of the relaxation of the molecular stretching. For example, in a
moulding using ABS, the shrinkage ranges between 0.4 to 0.7% in the direction
of flow, and between 0.3 to 0.5% in the transverse direction. However, glass-
reinforced materials are opposite to unfilled materials because the glass fibres
inhibit the shrinkage in the direction of orientation/flow. Thus, for glass-filled
thermoplastic polyester for a wall thickness of 2.5 mm (the shrinkage depends
on the wall thickness), the shrinkage in the flow direction is 0.25-0.35%, and in
the transverse direction 0.5-0.7%. Crystalline thermoplastics, such as
polyethylene, polypropylene or polyamide 6.6 exhibit greater shrinkage from
the melt (1.5-2.5%) than do amorphous plastics, such as polystyrene or
poly(methyl methacrylate) (0.5-0.8%). Some guidance on achievable toler-
ances for plastics moulding is provided in BS 2026; 1953: BS 4042; 1966: DIN
16901; 1973: and by materials suppliers.
Dimensional tolerances of mouldings produced entirely within one mould
part can be closer than for those produced across the parting line of the moulds
and subject, therefore, to position variations and the thickness of 'flash'.
Tolerances depend significantly on the type of material, shape and size of the
component and degree of control of the process. Closer tolerances than those
generally achieved, (usually monitored after at least 24 hours' conditioning)
can be obtained by choosing materials exhibiting low shrinkage and low
moisture absorption, and by processing them under strictly controlled
conditions (with the processing equipment shielded from draughts, for
example).
2.4 Importance of economics of processing in design

This important topic will be introduced by reference to the manufacture of a
case for electrical equipment used in civil engineering (Figure 2.16). The cable
avoidance tool (CAT) enables the underground track of power cables to be
traced, and hence there are fewer accidents when excavating. Several produc-
Figure 2.16 The Cable Avoidance Tool is made by Electrolocation Ltd., Bristol. It was designed
by B.I.P. Ltd., Streetly, West Midlands, and is moulded by Brettel and Shaw Ltd., Old bury
tion methods can be compared and the costs estimated for producing
approximately 1000 units per annum, the estimated market for CATs. This
component can be shaped using either blow moulding or rotational moulding
in one operation. Otherwise, it can be formed in two parts and assembled later,
the parts being injection moulded, thermoformed or manufactured using hand
lay-up or spray techniques. Thermoforming, in particular vacuum forming,
lends itself to large simple open sections such as this. This size of product is
limited to the size of sheet available, but the equipment and moulds are less
expensive than those for injection and blow moulding. Fabricating articles in
plastics is similar to sheet metal fabrication; it is a very labour-intensive and
slow process.
Rotational moulding is suited to simple enclosed shapes like footballs, road
markers and tanks up to 3 m 3 capacity. The equipment cost can vary widely,
but moulds can be made cheaply and quickly from sheet steel.
The use of reaction injection moulding (RIM) of high modulus polyurethane
offers a cheaper process relatively to screw-fed injection moulding. The basic
dispense unit, with a couple of mould tools (aluminium or ideally inexpensive
epoxide, for such low production runs), and clamping press, works out cheaper
than for thermoplastic injection moulding equipment with a single steel tool.
Some of the slower-reacting polyurethanes give longer moulding cycle time,
but the dispense unit can be more fully utilized by feeding up to nine other
moulds/presses in a production cell. Although polyurethane raw materials are
twice the price of commodity thermoplastics, process energy requirements for
dispensing are greatly reduced, the reaction and mould filling being carried out
at or just above room temperature.
Table 2.5 shows the costing of these production methods. The costs of
rotationally moulded and thermoformed parts are considerably lower than for
other methods for an annual production of 1 000 units. It is also true that the
costs will vary with the size ofthe components, the moulding cycle time and the
complexity of a moulding. This costing also assumes that the equipment for
manufacturing the rotational moulding is simple and cheap. However, such
equipment may vary from very simple rotating parallel bars with gas jets
beneath, costing less than £1 000, up to a very advanced automated rotational
moulding equipment costing in excess of £100000. The cheap system has a
poor production rate (four mouldings per hour), is very labour-intensive and is
suited to small production runs, whereas the more expensive equipment has a
fast production rate (several mouldings per minute), is suited to lengthy
production runs, is mainly automatic and its output is similar to injection
moulding.
In general, there will be a most suitable production method depending on
shape, size and quantity required for any component. For instance, if
quantities less than ten are required, then it is cheap to fabricate from sheet.
For quantities between 10 and 500, hand lay-up techniques are economical.
The cost of producing a simple product weighing 200 g by different production
Table 2.5 Relative manufacturing costings for the production of CATs
Reaction ""'
tv
-
Injection Injection Blow Thermo- Rotational Hand
Assumptions moulding moulding moulding forming moulding lay-up Fabrication
Cycle time 80s 1 5min' 60s 3min' 1 h2 44min 3 3h

Maximum throughput
(units/hr) 45 12 60 20 2 1.36 0.33
Utilization (%) 65 65 65 65 65 65 65
Capital cost (£) 1800004 50000 5 300000 6 12000 7 2000 8 200 600
Installation
charge (£) 18000 10000 30000 600 1000
Original tooling
cost (£) 40000 7500 9 500 2000 2000 500
"C
r
Total outlay (£) 238000 67500 340000 13000 5000 500 600 ~
...,
'"
Hours worked n
for 1000 units 34 128 26 77 770 1 131 4615 '"s::
Direct labour 1 person per 1 person per 1 person per 1 person 1 person 1 person ...,~
(@ £3.20/h) 2 machines 2 moulds 2 machines tn
Setting ~
1 setter per 1 setter per 1 setter per 1 setter per
(@ £3.70/h) 10 machines 40 moulds 10 machines 10 machines
;;
r
Labouring 1 labourer per 1 labourer per 1 labourer per 1 labourer per 1 labourer per 1 labourer per '"
(@ £2.90/h) 10 machines 40 moulds 10 machines 10 machines 10 machines 10 machines
Depreciation
(% of capital)' 12,5 10 12,5 10 10 10 10
Machine tool
overhaul
(% of tool costs) 10'0 10 10 10 15 20
Plant maintenance
(% of capital) 4 4 4 4 4
Power rating
(kW) 90 45 80 16 10
Consumables £2.65" £20
Joining of body
(moulded sections) £3 each £5 each £3 each
Final assembly cost £3 each
Annual cost for manufacturing 1000 Units (£):
Direct labour 54 102 42 246 2464 3619 14786
Setting 13 12 10 28
Labouring 10 9 7 22 223 328
Supervision 12 4 4 3 16 164 241 984
Depreciation 29750 6750 42500 1310 500 50 60
Machine tool overhaul 4000 750 1000 50 300 100
Plant maintenance 7200 2000 12000 480 80
Power (@ 4.98pjkW) 157 72 13 105 22 38 235
Consumables 2650 2000
Finishing costs 3 000 5000 3000
Total cost
(£/1000 units) 44188 17349 55667 5174 3769 6338 16047
Manufacturing cost ~
(£/unit)14 44.188 17.349 55.667 5.174 3.769 6.338 16.047 ;I>
Notes:
~
;:r
1. Two mouldings each. '"
2. Two moulds rotated simultaneously. ~
3. Minimum of one gel coat, and three layers of glass cloth/resin (@ 7 min per layer).
4. 500 tonne machine.
5. A RIM dispense unit normally will feed several moulds in separate presses, via a ring main and manifold system. Price here is based on equipment needed
"m
for two tools, each with a double cavity. ~
6. 30 litre capacity.
7. 1.5 x 1 m forming area.
8. Rotating drums over gas jets.
9. Estimates based on aluminium alloy tooling (5 000 to 25000 units output). Cost will be reduced using epoxide tools for short run production, although
their life will be less (250 to 1000 units).
10. One tool used after 10 mouldings.
11. RIM of PUs will include the cost of consumables, e.g. up to 25% of total moulding weight, release agent, tools and wash solvents.
12. One-fifteenth of direct labour.
13. RIM requires little energy for heating purposes, since it does not involve a melt process.
14. The polyurethane and glass-reinforced polyester materials will be 2} to 3 times the price of the LDPE materials used in the other processes. In some
processes, the product will have to be made into two parts, which are then joined by an epoxide or urethane adhesive, or ultrasonic welding. .j:>.
*Depreciation of capital equipment is based on a payback period of 8-10 years. However, current cost accountancy practice assumes payback in under 5 years; w
PU processing equipment is often estimated on the basis of a 2-year payback period.
t
1000
Note:
1. Rotational moulding using
very simple equipment
2. Rotational moulding using
sophisticated equipment
100
'"d
t-<
:>
ti '"
0 ::l
()
(")
-
'c::> '"
~
10
~
:;
t-<
'"
10 10 2 10 3 104 10 5 10 6
annual production-units
Figure 2.17 Comparative production costs for 200 g component
1·5
1·
o~ ____ ~ ____ ~ ____ ~ ____ ~
103 104 10 6 10 7
annual production
Figure 2.18 Comparative production costs for a 5-gallon drum
1. Injection moulding
2. Blow moulding
3. Rotational moulding
methods and for different production quantities is shown in Figure 2.17, but
this can only be used as a guide, and it is important that designers should
consider the product shape, size and production quantities before deciding on
one method or another. In fact a cost-effective product can be produced if a
cost analysis of several processes is conducted at this stage. Further details of
cost versus production quantity are discussed by Johnson [2], and two
examples are shown in Figures 2.18 and 2.19.
The annual production of mouldings required for the CAT indicated that
the most effective manufacturing method would be either GRP hand lay-up,
thermoforming or rotational casting, but experience had proved that GRP
6
-- 2
1;) .,......... ...... ..................
....... ........
...8 4 ..... .....
....
'c
:0 3· . . . ·... ·_.- ._._._ ..::; . . .
2
o~ ________ ~ __________ ~
104 10 5
annual production
Figure 2.19 Comparative production costs for a 55-gallon lidded drum
1. Injection moulding
2. Blow moulding
3. Rotational moulding
was not satisfactory because the cases were, in fact, too expensive to produce.
Thermoforming was possible, but this manufacturing method causes thinning
at corners and in deep sections, and the mouldings would need to be joined
around the circumference. Rotational moulding provides a sealed one-piece
unit which is more robust than the thermoformed part.
For completeness of these comparisons, reaction injection moulding (RIM)
has now been included in this new edition. Thus the case for RIM is developed
on a hypothetical basis, particularly with the need to use an alternative
polymer (low-density polyethylene being replaced by high-modulus
polyurethane, three times more expensive, as the product material). In the
USA, RIM and RRIM processes are used in direct competition to thermoplas-
tic injection moulding in the automotive industry, for example for vehicle
bumpers (fenders) at 5-20 kg shot size. To produce heavier plastics compo-
nents, basic RIM dispense machinery will be cheaper than that for thermoplas-
tics, (£110 000 compared to £300000 with closed-loop control), and with
cheaper tooling costs (£150000 compared to £250000). Until the early 1980s,
cycle-times for polyurethane-RIM ranged from 3-10 minutes, (application of
release agent contributing significantly), compared with 30-120 seconds for
thermoplastics. To their advantage, polyurethanes are processed at near room
temperature, saving on process energy requirements. The recently introduced
polyurethanejpolyurea systems have reaction rates which permit cycle times
of 45-120 seconds, and with the promise of a new generation of polyurea-
RIM, cycle times may be reduced to less than 30 seconds. Therefore, a decision
that must be made by the designer, often in conjunction with the technologist,
is whether production numbers, process costs and property requirements will
justify the use of high-cost raw materials.
References
1. Rooke, D.P. and Cartwright, DJ. Compendium of Stress Intensity Factors. HMSO, London
(1976).
2. Johnson, N.C. Cost comparison of rotational casting with injection moulding and blow
moulding. Brit. Plast., July 1974, p.376.
Further reading
Ogorkiewicz, R.M. (ed.), Engineering Properties of Thermoplastics, John Wiley, New York (1970).
Powell, P.C., Plastics for Industrial Designers, Plastics Institute, London (1974).
Williams, J.G., Stress Analysis of Polymers (2nd edn.), Ellis Horwood, Chichester (1980).
Powell, P.c., The Selection and Use of Thermoplastics, (Engineering Design Guides No 19),
Oxford University Press (1977).
Monk, J.F. (ed), Thermosetting Plastics: Practical Moulding Technology, Godwin [Longman
Group] London (1981).
Ogorkiewicz, R.M. (ed.), Thermoplastics: Properties and Design, John Wiley, New York (1974).
Ehrenstein, G.W. and Erhard. G., Designing with Plastics, Hanser [John Wiley] (1984).
Morton-Jones, D.H. and Ellis, J.W., Polymer Products; Design, Materials & Processing, Chapman
and Hall, New York (1986).
Powell, P. C., Engineering with Polymers, Chapman and Hall, New York (1983).
3 Styrene plastics
3.1 Polystyrene
During the 1939-45 war, supplies of natural rubber were denied to the
Western Allies by the Japanese occupation of Malaysia and other areas
producing natural rubber in the Far East. As a substitute, butadiene-styrene
synthetic rubber was urgently manufactured on a large scale, requiring the
manufacture of styrene on a considerable scale. At the end of the war, with
natural rubber freely available, the demand for synthetic rubber was reduced,
and the styrene plants were sold cheaply to the chemical industry. Styrene is
prepared by the Friedel-Crafts reaction between benzene and ethylene to
yield ethylbenzene, which is dehydrogenated to the monomer. It is not an
important chemical, except as a constituent of polymers, which are produced
by mass, solution or suspension polymerization, usually the last; emulsion
polymerization gives polystyrene latex. The quality of the polymer is
monitored by softening point, solution viscosity of a 2% solution in toluene,
and the proportion of methanol-soluble material. The softening point is
particularly affected by residual monomer, as is odour and the acceptability
for food contact applications.
Although polystyrene (PS) is a commodity plastic, much of the recent
growth has been in the modified grades; however, crystal polystyrene, (so-
called because of its sparkling appearance, and not implying that it is
crystalline), is available in a number of variants of different molecular weight.
These include general-purpose-a compromise between high molecular
weight for good mechanical properties and low molecular weight for adequate
flow; high molecular weight-for better impact performance; low volatiles-
increased softening temperature by up to 7°C; and easy flow-polymer of
lower molecular weight, plus internal lubricant.
The commercial plastic is non-crystalline, with a softening point of
approximately lOO°e. The low softening temperature and the amorphous
nature of the plastic mean that PS is one of the easiest plastics to mould, since
temperature may be used to reduce the viscosity to acceptable levels. However,
PS tends to degrade by depolymerization at temperatures above 150°C, so
that long dwell times in the melt should be avoided. Further, due to its ready
mouldability, there is a temptation to use long flow paths, and low mould
temperatures, for economy in cycle time, resulting in high residual strain in the
mouldings, with disastrous consequences on the strength. Other processing
advantages accruing from the non-crystalline nature are lower mould

shrinkage than for crystalline plastics, and a low heat content (enthalpy) to the
processing temperature, again compared with crystalline plastics.
Since polystyrene is amorphous, it is transparent unless insoluble additives
are used, and for the same reason it is soluble in aromatic solvents and
chlorinated hydrocarbons, and has a strong tendency to stress-solvent crazing.
As expected for a hydrocarbon polymer, PS has low water absorption and
excellent electrical properties. The specific gravity is 1.07 and the plastic is hard
and brittle; the strength is not exceptional, with pronounced stress-crazing
prior to fracture. Polystyrene is susceptible to degradation by UV radiation
(weathering); it is also flammable, burning with a yellow, sooty flame.
The properties militate against the use of this plastic in critical engineering
applications, but PS is widely used in decorative and commodity packaging;
examples are cosmetics and foodstuffs. An engineering use is approached in
lighting fittings, where evenness and intensity of illumination are important,
for instance in bookshops. There have been many trivial and transient
applications resulting from the easy processing, rigidity, transparency and
relatively low price.
Polystyrene has suitable rigidity and high-temperature performance to
enable it to be formed into attractive light fittings, especially covers for strip
lighting. However, the designer should be aware ofthe limited resistance ofthe
material to UV radiation, which may limit its use with high-intensity
fluorescent tubes. Furthermore, when PS is stressed, there is a tendency for the
material to craze at stresses considerably lower than that for failure; crazing is
visually unacceptable. However, PS is suitable in lighting fittings because of
the low stress involved and the minimal impact abuse; nevertheless, sharp
corners should be avoided and generous radii given to reduce the risk of
premature failure.
For the highly competitive lower-priced cosmetics market, the packaging is
often used to sell the product; thus it has to look attractive without increasing
the selling price significantly. For an attractive product, the essential
requirements are a good surface finish and colouration, whilst only a small
amount of post-moulding distortion is acceptable; with the added property of
transparency, PS is a reasonable choice. These same qualities are involved in
the marketing of confectionery, but here it is the higher-quality end of the
market which has adopted plastics packaging. This is preferred to the
paperboard used at the lower end of the market: an example is shown in
Figure 3.1. For economic reasons the melt temperature and the mould
temperature are sometimes kept at low levels to obtain short cycle times: this
leads, however, to stresses frozen into the moulding. These are detrimental to
the mechanical properties and could result in premature failure. It is desirable,
therefore, to mould with higher mould and melt temperatures, with conse-
quently increased cycle times to reduce the moulded-in stress: a balance must
be reached between cost and performance.
STYRENE PLASTICS 49
Figure 3.1 Crystal PS is used for the packaging of high-quality confectionery
3.2 High-impact polystyrene (HIPS)

The main deficiency of polystyrene is its brittleness; this may be improved by a
number of techniques, which are generally applicable in polymer technology:
(i) Increasing the molecular weight: this inevitably increases the melt
viscosity which, in turn, may result in higher residual orientation in
mouldings and extrudates, with consequent deterioration in impact
strength
(ii) Planar orientation: this is applicable only to films, and, more recently,
pipes and bottles
(iii) Addition of plasticizer: only a limited improvement in toughness is
obtained, and there are significant losses in softening temperature,
rigidity and strength
(iv) Copolymerization
(v) Polymer blending: a variety of blends is possible - homogeneous blends
with other plastics of good impact strength, composites involving fillers,
and blends with rubbers.
Although there is limited scope for improving impact performance by
increasing the molecular weight, (iv) and (v) provide the main methods by
which the toughness of polystyrene is improved.
The addition of rubbers to PS is widely practised; the secret of obtaining
good impact behaviour without compromising rigidity is that the blend
should be heterogeneous. Butadiene-styrene rubber (SBR) may be blended
with PS, but this can lead to molecular mixing, resulting in plasticization and
little improvement in toughness. Better results are obtained if the rubber is

dissolved in styrene monomer and the resulting syrup polymerized, leading to
a dispersion of rubber particles in polystyrene. The greatest improvement in
toughness is obtained if rubber latex (polybutadiene is preferred for good low-
temperature properties) of particle size 0.1-1.0!lm is reacted to give a grafted
coating, and the product then added to styrene monomer which is poly-
merized. Usually 10-20% rubber is involved. The structure of this composite
consists of a PS matrix, with inclusions of discrete rubber particles, some of
which themselves contain smaller particles of polystyrene. The rubber phase is
rendered visible in the electron microscope by staining with osmium tetroxide
or iodine; the particles are too small to be seen by light microscopy, although
they scatter light, leading to opacity.
The easy processing characteristics of polystyrene are retained in HIPS;
indeed, for pre-gelled rubber particles, injection moulding is facilitated, but if
they are larger than 10 !lm, surface finish deteriorates. Thermoforming,
especially vacuum forming of extruded sheet, is a favoured way of shaping
simple objects, e.g. disposable beakers for drinks, and more complex
engineering structures, such as refrigerator liners.
The modification of PS with rubber results in a considerable increase in
impact toughness, by an order of magnitude, but with deterioration in other
properties: 5-15°C in softening temperature and 20-40% in rigidity and
strength (see Table 3.1). The ageing behaviour is also worsened by inclusion of
rubber, but incorporation of antioxidant largely restores the situation.
These properties allow the use of HIPS in many applications, especially
where impact abuse is encountered; however, the low softening temperature
offers some limitation. Applications include refrigerator liners and fittings,
toys, games and sports equipment, and radio and electrical equipment
housings. As with PS, design with HIPS has been largely empirical, as in the
following case study.
There have been several examples ofthe unsatisfactory use ofPS, because of
the brittle nature of the material; the application in toys is typical. Children
frequently abuse their toys and thus a good impact performance is essential.
General-purpose polystyrene (GPPS) breaks and exposes a sharp edge as an
additional hazard. The advent of HIPS allowed the good features of PS to be
retained, with the additional benefit of toughness at room temperature (the
toughness falls dramatically below - 20°e), for only a small increase in
Table 3.1 Properties of PS, HIPS and SAN
PS HIPS SAN
Tensile strength (MPa) 34-51 27-43 65

Elongation (%) 4 20-50 2.5
Impact strength (Jjm) 10-20 45-65 10.5
Vicat Softening Temperature (0C) 90 85 102
STYRENE PLASTICS 51
material cost. Several materials could be considered for the manufacture of
toys: impact modified PP and HDPE are durable and appear superior to
HIPS. However, HIPS is frequently preferred for the following reasons:
(i) PS can be easily joined using solvent adhesives
(ii) Amorphous materials have less shrinkage, and take more detail from the
mould surface
(iii) Painting and plating are much easier for HIPS.
Many of these qualities of HIPS are implicit in the toy shown in Figure 3.2.
Refrigerator liners are simple open-section parts which could be made by a
variety of shaping methods. However, the comparatively small numbers
required for anyone design precludes techniques such as injection moulding.
Thermoforming is more favoured, but this restricts material choice; further,
the material must stand abuse at 4°C, and withstand thermal cycling between
this temperature and ambient conditions. Crystalline polymers are more
difficult to handle since their melt strength is low. PVC thermoforms
satisfactorily but has generally less suitable low-temperature properties.
The liner in Figure 3.3 is manufactured in sheet of 3 mm thickness which is
heated on both sides and blown with compressed air. The part is subsequently
shaped on a male former by vacuum. A minimum thickness of 1 mm is retained
after moulding to ensure robustness, with the overall thickness 1.5-2 mm.
When the liner is in position in the body of the refrigerator, the space is injected
with polyurethane foam, giving rigidity in the protruding features of the liner
and thermal insulation.
The low-temperature impact performance of HIPS is unsuitable for deep-
freeze applications, where ABS is preferred; the penalty is that ABS is
significantly more expensive than HIPS.
Figure 3.2 The Action Man Motorcycle manufactured by Kenner Parker (formerly Palitoy).
Coalville, Leics
Figure 3.3 Refrigerator liner manufactured by Electrolux Ltd
As we have seen, HIPS is frequently in direct competition with grades of

polypropylene.
3.3 Styrene copolymers

Although styrene has been copolymerized with a wide variety of comonomers,
only the systems involving butadiene and acrylonitrile are of commercial
importance; the former are employed as rubbers and, at higher styrene
contents, as coating resins and rubber reinforcing agents. They will not be
considered further. In the styrene-acrylonitrile system, one particular copoly-
mer is unique, that containing 65-70% styrene (SAN), which is a preferred
composition in respect of properties, and especially since it is easily
manufactured. The reader is referred to other texts for details of copolymeriz-
ation mechanisms, but it should be mentioned that it is rare to find copolymers
formed at the same ratio as the comonomer feed; the copolymer quoted is such
a case. Compositions containing more than 80% acrylonitrile have also been
developed as barrier resins; they are melt processed but their progress is
retarded by fear of the toxicity of residual acrylonitrile monomer.
Incorporation of acrylonitrile into a styrene polymer increases softening
point and toughness, presumably by increasing the interchain attraction. For
the same reason, resistance to non-polar solvents, such as fats and oils, is
improved. Some data are given in Table 3.1. To summarize its properties, SAN
has a softening point some lOOC higher than that ofPS; is transparent, but with
a tendency to yellowing, particularly on weathering; and is somewhat tougher
and stronger than polystyrene. SAN is used for drinking tumblers, jugs and
other transparent domestic ware, and for transparent and reasonably tough
STYRENE PLASTICS 53
covers for domestic, electrical and automotive equipment, as shown in the
following case study.
Many manufacturers of record players have supplied transparent covers for
their equipment, so that record and mechanism are visible. A cover may be
abused or dropped and so requires adequate impact strength. Further, it is an
aesthetic part, so that distortion must be low, and preferably undetectable. For
transparency, the choice is sensibly limited to amorphous polymers, which
also have good after-moulding dimensional tolerances and low distortion.
SAN was chosen as it has better impact properties than PS, retains the easy
flow of PS, and is cheaper than PMMA. The characteristic yellow tint of SAN
is usually masked by adding dye to produce an overall effect similar to smoked
glass. The moulding is centre-fed into the underside of the top, but since the
sprue leaves residual marks and flow lines, these have been disguised by
positioning the decorative insignia.
Recently, a new family of styrene copolymers has been marketed, combining
a high transparency (although marginally inferior to PS) with good impact
properties and rigidity. They are block copolymers of styrene and butadiene,
containing a preponderance of the former (70-80%); this constitutes the
transparent matrix in which submicroscopic domains of (block) poly-
butadiene are dispersed. These provide energy-dissipative mechanisms during
impact, but are sufficiently small not to scatter light appreciably, although a
'blue haze' can be discerned. As with other block copolymers, processing and
subsequent behaviour may not be straightforward. An example, a transparent
component for a toy, is shown in Figure 3.4.
Figure 3.4 Transparent component for a toy manufactured by Kenner Parker (formerly Palitoy),
Coalville, Leics
3.4 ABS plastics

The availability of SAN, of greater toughness and higher softening tempera-
ture than PS, gives an opportunity for composites analogous to HIPS. The
polar copolymer allows the use of polar butadiene-acrylonitrile rubber which,
pre-gelled in a blend at 20% content, gives a composition of very high impact
strength. A product with superior low temperature performance is obtained
from polybutadiene latex, grafted with a SAN-compatible coating on to which
the SAN is polymerized. Following much development work by the manu-
facturers, a wide selection of grades of ABS is marketed, sharing very great
resistance to impact abuse, with a softening temperature similar to that of PS.
ABS plastics are usually opaque, although a transparent version can be made
by matching the refractive indices of the resin and rubber phases. This is,
however, inferior to ABS and more expensive, so is not widely used.
The dominant property of ABS plastics is the very high impact strength,
which is coupled with less desirable features, such as a softening point similar
to that of PS, and comparatively low stiffness and strength for structural use.
'"
:::l
:::l
""C
o
E
0·01 100 104

time (hr)
Figure 3.5 Tensile creep modulus of ABS
high impact ABS
~c. 200
.§
""C
Q)
.s::
o<:
<J
~::::::~~::::::::::::~(:SA:N~)=-
O[
-40 -20 o 20
temperature CC)
Figure 3.6 Impact properties of ABS

STYRENE PLASTICS 55
~
"'
Il.
~
Q)
".~
0..
E
"'
III
III
~
iii
C>
c:
.~
c:
2!
<i
0
10 4 1O ~ 10 6 10 7
number of cyc les to failure
Figure 3.7 Fatigue properties of some styrene plastics
They retain, however, the excellent injection moulding behaviour of styrene

plastics, particularly good melt flow, low mould shrinkage and excellent
surface finish . Properties relevant to design are given in Figures 3.5- 3.7. The
rigidity can be improved by reinforcing fillers; glass fibre composites appear to
be the most popular, although the surface finish and toughness are compro-
mised. Attention is drawn to Figure 3.7, which records that the fatigue
behaviour is not comparable with the excellent impact property.
Applications of ABS plastics reflect the processing behaviour and the high
impact strength: vacuum cleaner covers, carpet sweeper housings, lawn mower
housings, telephone handsets (replacing PMMA which in turn replaced PF),
and hair-dryer housings of higher softening temperature than HIPS. They also
Figure 3.8 Flymo Hovermower™ cover

find application where good dimensional tolerance, coupled with good surface
finish and adequate mechanical properties, is required: car instrument clusters,
car fascias and trim.
Typical of the applications of ABS is the Flymo Hovermower™ cover,
shown in Figure 3.8. This component, which replaces a similar unit in sheet
metal, offers many advantages. It is aesthetically attractive, and does not
require painting for protection. Impact blows, inflicted by missiles picked up
by the rotating cutters, do not produce damage by fracture or denting. The
unit is injection moulded and a good surface finish is an added attraction. All
the fitting elements are included in the moulding, so no further fabrication is
necessary, in contrast to its sheet-metal predecessor.
As a further case study, for many years the main body component of upright
vacuum cleaners has been manufactured as a metal casting, since it was
thought that metal was the only material able to withstand the abuse inflicted
by the user. However, the cost of casting metal has increased dramatically in
the last 25 years, and plastics have become increasingly attractive on economic
grounds. The component is used to locate accurately several parts which
interconnect, so that close tolerances are essential. A further requirement for
this product is good visual appearance, since it is the part which customers
examine most closely in the showroom. The choice of material depended
mainly on impact performance. ABS is outstanding in this respect, and has
suitable strength and good moulding properties at an economical price.
Modified poly(phenylene oxide) - see later in this chapter - is also suitable.
The cheaper ethylene and propylene polymers suffer from poor dimensional
stability and unacceptable warping for this application (see Chapters 5 and 6).
Polyamide 6.6 is a possibility, but the material is crystalline and, being
sensitive to water content, will distort to a greater extent than other materials.
Polycarbonate is very suitable, but is expensive.
The change from cast aluminium to ABS for this component required a
complete redesign of the base to allow for the different properties of plastics,
and the greater detail possible in the moulding operation. Several ribs were
incorporated in the new design, including variations in wall thickness to
withstand impact, short- and long-term loads. Such a design with varying
section may lead to distortion and surface marks; the polymer is injected
through several gates positioned in the central hole, thus preventing the
appearance of surface marks which would result from a gate situated at the
surface. Moulding the component to accurate dimensions required close
control over the moulding conditions, under which circumstances a tolerance
of 0.1% is possible, although normally, on parts of75 mm in size a tolerance of
0.2-0.3% is more usual.
3.5 Polystyrene-poly(phenylene oxide) blends

A product range of increasing commercial importance is based on blends of
PS with poly(phenylene oxide) (PPO). The latter is in fact the dimethyl
STYRENE PLASTICS 57
2· 5 r - - -__
co
a...
(!)
~ 2·0 23'C
:J
"0
o
E 1.5
66'C
1·0
10 10 2 10 4
time (hr)
Figure 3.9 Tensile creep modulus of modified PPO
.§. 300
:;..
.<:
0,
c
~ 200
<J)
.-
(,)
co
C.
.S 100
"0
Q)
.<:
(,)
0
c
-50 0 50 100
temperature ('C)
Figure 3.10 Impact properties of modified PPO
<0
a...
(!)
~
--=::::--
3
<J)
:J HIPS medium impact
:J
"0
0
2 ____ - - - - PPO modified
E ~BSregUlar
~ HIPS super high impact
:J
X
Q)
;:
OL-_--'-_~~_ ........._---'_ _........._

0·1 10 102 10 3 10 4
time (hr)
Figure 3.11 Flexural creep modulus data at 20 G

e for some styrene plastics
Figure 3.12 Triumph TR7 fascia moulded in modified PPO
homologue, which is used to restrict linkages in the polymer chain to the para-
position. PPO homopolymer is a high-strength, reasonably tough, non-
crystalline thermoplastic which is very difficult to process. It is also compara-
tively expensive. Somewhat surprisingly, PPO is miscible with PS on a
molecular scale, and the blends are also capable of being further toughened by
techniques analogous to those used in HIPS and ABS. Design data are given in
Figures 3.9- 3.11. Typically, grades with softening points some 30- 40DC
higher than polystyrene are available, with rigidity and strength approxi-
mately 50% higher than high-impact ABS, and with similarly enhanced long-
term behaviour. The processing characteristics are inferior to those of ABS,
particularly the melt flow, which is restricted; in consequence, it is usual to
work at very high melt temperatures (280- 300 C), and to use multiple gating.
D
A property unusual in styrene plastics but exhibited by these blends is that

they are self-extinguishing when ignited.
The blends have the good dimensional tolerance of amorphous plastics in
general and of styrene-based plastics in particular, and are finding increasing
use in car components, television set backplates, transformer cases, electrical
equipment housings, etc. They can be made in structural foam grades, and as
glass-fibre and mineral-filled composites. Further, the foams may be reinfor-
ced, giving a diverse family of materials, with many actual and potential uses.
Foamed modified PPO business machine components are large mouldings
which need rigidity to retain several parts of the equipment (such as the
keyboard), good dimensional stability and very good tolerances. Other
performance requirements are good impact resistance, pleasing appearance
STYRENE PLASTICS 59
and cost effectiveness. A structural foam based on a PPO-PS blend has been
found very satisfactory at a density of 900 kg m - 3 with an integral skin.
As a concluding comment it must be pointed out that, in considering
styrene-based plastics for particular applications, the poor solvent resistance
might be a limitation. Simultaneous application of stress, in the presence of a
solvent, may give premature failure due to environmental stress cracking.
These comments apply equally to PS, HIPS, ABS and the PPO-PS blends.
4 Other amorphous thermoplastics
Amorphous thermoplastics were some of the earliest plastics, excepting

polycarbonate, to find general acceptance; indeed, cellulose plastics were the
first thermoplastics available commercially, and poly(methyl methacrylate),
(PMMA), was a commercial product in the 1930s. Their continued application
some 50 years later is a comment on their usefulness, and on their properties
compared with those of polystyrene, since PMMA is almost twice the price of
PS, and the cellulose plastics are significantly more expensive than PMMA.
Polycarbonate, a development of the late 1950s, is some three times more
expensive than PS, and so finds use in critical applications where performance
rather than cost is the criterion of acceptability. There are other amorphous
thermoplastics with yet more advantageous properties which have not
reached the status of commodity materials; a selection of these with elevated
service temperatures is reviewed in a later chapter.
In addition, one of the most versatile and widely used plastics, poly(vinyl
chloride), (PVC), should also be included in this category. Since a small
amount of crystallinity affects its behaviour, however, it will be considered
separately in Chapter 8.
4.1 Poly(methyl methacrylate), (PMMA)

PMMA is available in two forms, sheet and moulding powder, which are
manufactured by very different processes and which are shaped by different
techniques. Sheet is frequently made by casting a syrup, consisting of
preformed polymer is methyl methacrylate monomer, with added initiator, in
glass cells, the polymerization being carried out over many hours. Alterna-
tively, polymerization is carried out in an extruder, the sheet being shaped by
an appropriate die on leaving the extruder. Whereas the former process can
produce polymer of very high molecular weight, the latter method requires
that the molecular weight be controlled to allow of die shaping. Moulding
powders and general extrusion grades are made by suspension polymeriz-
ation, involving molecular weight control by added chain transfer agent, often
dodecyl mercaptan.
The cast sheet cannot be processed by methods generally applicable to
thermoplastics; however, it can be thermoformed by vacuum, blowing or plug-
assist methods. The deformation imparted is almost entirely high elastic strain,
and the original sheet is regained if the shaping is heated above the softening
OTHER AMORPHOUS THERMOPLASTICS 61
temperature. This concerns the designer; he should be aware that at
temperatures some way below the equilibrium softening temperature, the
shaping will start to 'demould' or revert, as the residual stress lowers the
effective softening temperature. Moulding powder or extrusion-grade polymer
is processed conventionally, but has a somewhat higher melt viscosity than PS
or the crystalline thermoplastics, and therefore requires more robust equip-
ment. The viscosity is also more temperature-dependent than for most
thermoplastics melts, necessitating good temperature control of the equip-
ment. The plastic should be dry before processing, otherwise 'splash marking'
may occur. In common with PS and all other amorphous thermoplastics, the
mould shrinkage is low (0.8%).
The principal properties of PMMA are summarized below. The absorption
of visible light is zero and the light scattering so low that for most practical
purposes the transparency is perfect. (Signal attenuation is still significant,
however, in the context of communications transmission lines.) Even with
'perfect' transparency, it should be remembered that reflective losses inevitably
occur when light enters a material of different refractive index. PMMA is a
material of high strength but is brittle, failing at low elongation. The very high-
molecular-weight sheet polymer is stronger than the moulding grade, and
significantly tougher. Data are given in Figure 4.1, which also records the
crazing stresses for loading in air; the superior performance of the sheet
material is again evident. This is also shown in the impact strength, which is
some 50% higher than for the moulding grade, although the fracture is still
brittle (Figure 4.2). Creep data are given in Figure 4.3. PMMA has a hard
surface and is reasonably scratch-resistant; the surface hardness is amongst the
highest for thermoplastics, 9H on the pencil scale. The softening temperature is
slightly higher than that of PS at 105-120°C, being depressed by absorbed
moisture and residual monomer. PMMA is very resistant to UV radiation and
to weathering. This excellent behaviour may be impaired by residual stress in
the shaping, which can add to the moisture absorption and desorption stresses
70 cast sheet necking failure stress

~ 60
~ 50
'"'"
~ 40
'Cij
~ 30
·iii
c 20
S
10 moulding grade
0
0·01 0·1 10 10 3
time (hr)
Figure 4.1 Poly(methyl methacrylate): rupture stress in tension as a function of time

150r---________----
unnotcbed (sheet)
E
...,
.......
~ 100
C,
c:
l!!
ti
'U
III
Co notched (sheet)
.§
notched (moulding powder)
-20 o 20 40
temperature ("C)
Figure 4.2 PMMA cast sheet and moulding powder: impact strength vs. temperature (notch tip
radius 2mm)
1.0' /a=20MPa
0.8~
~
of!c: 0·6
ti
0·4, _ _-
0·2
10 100 1000
time (hr)
Figure 4.3 PMMA moulding powder: creep in tension
and lead to crazing. One of PMMA's least attractive properties is that it is

readily flammable, with burning drips, restricting the use of the unmodified
plastic in building applications; flame retardant grades have been developed,
however, with improved performance in this respect. PMMA is resistant to
salts, alkalis and dilute acids, detergent solutions, greases and oils, but many
polar solvents, including alcohols, ketones and chlorinated hydrocarbons, are
partial or complete solvents and promote crazing, particularly in stressed
samples.
Applications are principally concerned with transparency and light transfer,
with good weathering resistance, and with high surface hardness and
durability. They include glazing in aircraft and other transport, transparent
guards and covers, baths, wash-basins and sanitaryware, and rear-light
assemblies for road transport. The last two applications exemplify the use of
sheet and moulding grades respectively.
Producing large shapings frequently involves thermoforming techniques
because large objects can be shaped easily and cheaply by this method.
Amorphous plastics are more suited to this production method, and it is
therefore predictable that acrylic sheet should be used in the manufacture of
large thermoformed shapings such as baths. PMMA cast sheet has become
established as the most suitable material because it has a higher softening
point than PS or HIPS, and is rigid and hard, so that the surface does not
scratch easily. Furthermore, it is cheaper than polycarbonate, does not absorb
much water, and is unaffected by the numerous chemicals used in baths. A
further advantage is gained by the use of cast sheet, because the strength is
increased by the orientation in the direction of draw.
A rear-light assembly (Figure 4.4) consists oftwo main parts: the lamp body
which contains the reflective pockets and retains the bulbs, and the cover,
comprising several different colours in one moulding, or several components
of different colours. The assembly is held together by self-tapping screws,
which locate through the body and grip into bosses moulded into the lens (or
vice versa). PMMA is used because of its good transparency, good colour
retention, satisfactory chemical resistance and adequate impact performance
at a moderate price. PS is cheaper but is very brittle, has poor solvent
resistance, is attacked by petrol and tends to craze at comparatively low
stresses. Polycarbonate is a very tough and rigid material with good
transparency and, with the addition of UV stabilizers, is unaffected by
weathering. However, it is more expensive than PMMA, and petrol may be a
stress cracking hazard; polycarbonate is sometimes used in lenses requiring
superior impact performance, and which generally do not come into contact
with petrol (front signal and parking lamp lenses). Cellulose acetobutyrate is
much tougher than PMMA, has good clarity, but is more expensive, has a
lower working temperature, scratches easily and does not weather well. In the
past, lenses were made separately, hot welded or dipped together, then
Figure 4.4 Automobile rear lens, moulded by Lucas Electrical Ltd., Birmingham
assembled to the base. This involved several assembly operations, and the unit
was not always watertight. Currently, lenses are either moulded by two-colour
machines (with two or more injection cylinders), or are moulded individually,
then placed in another mould and encapsulated in clear polymer.
4.2 Cellulose plastics

Cellulose is a polymer which occurs abundantly in nature, constituting about
one-third of the vegetable matter of the world. Cotton is almost pure cellulose,
whereas wood contains about 50% of the polymer. Cotton linters and wood
pulp are the usual raw materials for cellulose polymers. The former is digested
at 120-150°C with dilute caustic soda, and bleached to give 99% pure
cellulose, and wood pulp cellulose is extracted by a variety of chemical
processes to a product of 88-90% purity, which can be enhanced by alkaline
digestion and bleaching.
The empirical formula of cellulose is C 6 H100S' indicating its probable
derivation from sugar (glucose, C 6 H 12 0 6 by elimination of water H 2 0);
indeed, the polymer can be hydrolysed to glucose. There is strong evidence
that the structural repeat unit is cellobiose. This structure implies three
hydroxyl groups per repeat unit (one primary and two secondary), with a
consequent sensitivity to water, although cellulose does not dissolve, since it is
crystalline and extensively hydrogen-bonded.
Exploitation of cellulose takes three routes: treatment to yield a tractable
intermediate, with subsequent regeneration of the cellulose, and the manufac-
ture of cellulose esters and ethers. The esters are the most important
derivatives of cellulose, although cellulose itself is employed as a filler in cross-
linked plastics, particularly urea-formaldehyde resins. Regenerated cellulose
was the earliest man-made fibre and is still extensively used; in film form,
cellophane was an early packaging film, now superseded by cheaper products
with technically more desirable properties.
4.2.1 Regenerated cellulose

A number of processes are available, of which the most significant are the
cuprammonium route and the viscose process; in the latter, cellulose is treated
with caustic soda to give 'alkali cellulose', which is reacted with carbon
disulphide to give 'cellulose xanthate':
cellulose-O. Na + CS 2 ~ cellulose-O-C-S. Na
II
S
cellulose xanthate
After forming into a film, the material is hydrolysed back to cellulose.

Cellophane is very permeable to moisture, which is a shortcoming for a
packaging film; the barrier properties may be improved by coating with
poly(vinylidene chloride).
4.2.2 Cellulose esters

As we have seen above, the structural repeat unit of cellulose contains three
hydroxyl groups which are available for chemical reaction, including esterific-
ation. As frequently found for reactions involving a crystalline polymer,
homogeneous reaction usually requires that the polymer be in solution. The
nitration of cellulose is, however, exceptional in that the reaction is progress-
ive, the extent of nitration depending on the strength of nitric acid employed.
Other esters of continuing commercial interest are cellulose acetate (CA),
cellulose propionate (CP) and the mixed ester, cellulose acetobutyrate (CAB).
Cellulose dinitrate is obtained by treating cotton linters with a mixture of
nitric acid, sulphuric acid and water (25: 55: 20), and treating the product with
alcohol. Camphor, a favoured plasticizer, is mixed into the alcohol-wet cake,
leading to the product 'celluloid', for which the most important application is
the manufacture of table-tennis balls.
The esters derived from organic acids are more important than the nitrates,
partly because they do not share the almost explosive flammability of the
nitrates. Acetylation of cellulose reduces the capability of hydrogen bonding,
decreases the polarity and increases chain separation; consequently esters with
substantial substitution are amorphous. The acetates can be obtained at
different levels of acetylation, but those at low levels are obtained by hydrolysis
of the triacetate, not by direct esterification. The usual levels of reaction range
from 2.2 for injection moulding grades to 3.0 for film and fibre applications.
CA requires plasticizer to reduce the softening temperature and enable
processing to be carried out without degradation: dimethyl phthalate and
triphenyl phosphate are used in this way. Variation of plasticizer content, level
of esterification and differences in the chain length of the parent cellulose lead
to a family of plastics differing in softening temperature, hardness, strength
and impact toughness. All grades are transparent, but are not particularly
resistant to weathering.
Cellulose propionate (CP) and cellulose acetobutyrate (CAB) are more
expensive than the acetate, but offer better dimensional stability (having lower
water absorption) and improved toughness. For each ester class, a variety of
grades is available, as with CA. Typical applications of CA, CP and CAB
include transparent packaging, lamp shrouds and table lamps, control
buttons, telephone dials, toys, tabular keys, spectacle frames and sunglasses,
decorative trim for cars, and domestic appliances. Handles, from tooth-
brushes to cutlery and tools, and hammer heads, provide significant outlets for
these plastics.
An important characteristic of cellulose acetate is its transparency; com-
pared with other transparent materials it has much better impact properties
Figure 4.5 Cellulose acetate screwdriver handles
than PS, PMMA, SAN and P 4MP (see Chapter 6), but is inferior to
poly carbonate, which is, however, more expensive. CA has been used for
screwdriver handles for many years; these are extruded into the required
profile, with ribbed or plain fluting, and cut to the desired length. They are then
machined to produce domed ends or collars on the handles; trade marks,
names, voltages and codes are hot-foiled or stamped afterwards. The
production of tool handles by this method is cheaper than by injection
moulding; the handles are produced in clear CA, so that they look attractive,
and the tight fitting of the screwdriver shank can be seen (Figure 4.5).
4.2.3 Cellulose ethers

Although a number of cellulose ethers are known, the ethyl derivative is the
only member finding plastics uses, mainly as a surface coating; others are
water-soluble and are used in food processing. Commercial ethyl cellulose
contains 2.15 to 2.6 ethyl groups per repeat unit and is obtained by treatment
of alkali cellulose with ethyl chloride. It finds use in compositions for the
strippable protection of metal parts.
4.3 Polycarbonate
Poly carbonates involve the simple carbonate linking groUP~C03~
although only one such material, that based on bisphenol A (diphenylol
propane), is important commercially. Structurally it is a polyester but, unlike
aliphatic polyesters it is reasonably resistant to hydrolysis, particularly in the
solid state, less so in the melt. Although polycarbonate (PC) is a linear polymer
with a symmetrical structure, the melt-processed material is reluctant to
crystallize, and PC articles and components are substantially amorphous and
consequently transparent if unpigmented.
Grades of polycarbonate are available for injection moulding and for
extrusion-based processes including blow moulding. As PC is a polyester and
is susceptible to hydrolysis, it must be dried before processing, care being taken
to keep the polymer dry in the hopper ofthe processing equipment. Compared
with PS, the melt is processed at higher temperatures corresponding to its
softening point 45°C higher. Further, the viscosity is less shear-dependent than
for most thermoplastics. There is an even greater temptation than with
polystyrene to process at a low temperature to reduce costs, but this leads to
high residual orientation with possible catastrophic effects on the mechanical
strength which otherwise, for properly designed and processed parts, can be
outstandingly good. Gross frozen-in stresses may be identified by immersion
of the mouldings in carbon tetrachloride, when such shapings develop
extensive cracking; alternatively, the stresses may be monitored by birefring-
ence measurements. Mould shrinkage is low (0.7%), and is reduced further by
incorporating glass fibres; this may lead to anisotropy, due to orientation of
the fibres in the flow direction, with consequent lower shrinkage (0.25%)
compared with the transverse direction (0.4-0.5%).
The mechanical properties of PC have been of the greatest significance in its
increasingly widespread application. Unusually for a rigid amorphous (glassy)
plastic, polycarbonate is generally tough, as shown by a variety of impact data
(Figure 4.6). However, great care must be exercised in the design of compo-
nents in this plastic, since a wide range offactors can lead to embrittlement and
premature failure; these include sharp cracks, (especially in thick sections),
frozen-in stresses, cyclic stressing and a number of organic solvents which
promote cracking. The deformation properties of PC are not particularly
sensitive to temperature until the softening region above 140°C is reached;
1000
E
--
2- ~
,,
.c: I
C. 600
,
c:
~
ti
.,
0
200 I
I
--!
Co
.§
-20 0 20 40 60
temperature ("C)
Figure 4.6 Impact strength of polycarbonate

50
strain (%)
Figure 4.7 Polycarbonate: isochronous stress vs. strain curves. 1000 hours
70
m
a..
~
~
'"'"2! 23·C
1;;
~ 40·C
·iii
I: 60·C
! 30 80·C
20
0·1 10 102 10 3 104
time (hr)
Figure 4.8 Polycarbonate: failure stress vs. time
isochronous stress vs. strain data for 1 000 hours loading are given in
Figure 4.7, and time-to-failure data portray a similar picture (Figure 4.8).
The other important attributes of polycarbonate are transparency (a quality
shared with all other unadulterated amorphous thermoplastics) and non-
flammability; the critical oxygen index is 25% for unfilled polymer. However,
with this index, it is likely that PC would continue to burn in a hot
environment. Also on the debit side, the chemical resistance is not outstanding,
and satisfactory weathering resistance is only achieved with additives.
The incorporation of fillers, particularly glass fibres, to enhance the rigidity
of PC is standard practice but, as might be expected, this has a deleterious
effect on the impact performance. Data illustrating the considerable improve-
ment in modulus consequent on glass fibre reinforcement are given in
Figure 4.9 and Table 4.1; the deterioration in impact strength is seen in the
same table.
The range of uses of PC has been increased considerably in recent years,
many of the new applications not depending on transparency and being based
30% glass-fibre reinforced
~ 6t---------~~~
c...
(,!) 5
(/)
:l
:l 4
"0
o
E 3
~ _ _ _ _ _ _ _~u!!.n~filled
~ 2
Ql
;;:
-40 o 40 80 160
temperature (·C)
Figure 4.9 Flexural modulus of poly carbonate vs. temperature
Table 4.1 Effect of glass fibre on polycarbonate
Glass fibre content Flexural modulus lzod impact strength

(%) (GPa) (Jim)
o 2.4 650 to 850

10 3.5 250
20 5.6 107
30 9.85 134
on composites, including foams. Blends of PC with other polymers are

renowned for their excellent impact performance: these include the totally
amorphous PC-ABS system and the partially crystalline blend with
poly(butylene terephthalate). The latter will be discussed more fully in Chapter
7.
Examples of applications may be cited for which different selections of
attributes are involved:
(i) Toughness and transparency. Bottles, ranging from feeding bottles to 25-
litre containers (sterilizability is an added advantage, although prolonged
boiling in water is detrimental to properties); protection shields or
partitions in taxis or police vehicles; vandal-resistant light covers and
illuminated signs; vandal-resistant roof lights; glazing likely to be
subjected to impact loads (for instance in quarry buildings); inspection
glasses in chemical plant.
(ii) Toughness and high softening temperature. Hair-dryer bodies; coffee
makers; spotlight housings; housings for car light assemblies.
(iii) Toughness and flame resistance. Aircraft interior fittings; switch boxes for
mines and quarries; high voltage plugs and sockets.
(iv) Stable and consistent electrical properties. These enable PC to be used
particularly under extreme environmental conditions in small electric
motors, casings for power rools and steam iron designs.
Figure 4.10 Polycarbonate component of vacuum cleaner manufactured by Electrolux Ltd.
An Electrolux suction cleaner (model Z345) has the motor and fan
assembly suspended between a rubber mounting and a bracket (Figure 4.10).
The motor assembly is forced into the rubber mounting and isolated from the
bracket by a spring. Thus the bracket is used to compress the spring, and is
loaded continuously throughout its life; furthermore, the cable feed mechan-
ism locates into the bracket, and two electric contact rings are incorporated to
enable the electricity supply to be connected between the rotating feed
mechanism and the stationary bracket. The electrical power can then be
connected to the motor. This component (Figure 4.10) requires good re-
sistance to creep, especially at localized temperatures above 50- 60°C, good
electrical properties, and good impact behaviour to reduce the possibility of
fracture if the cleaner is dropped accidentally. The dimensional requirements
are also critical, to within 0.15%.
Previously phenolic mouldings were used for a similar application in a
much simpler unit, but were not considered suitable in the present context
because of the detail required. Moulding grades of PF have poorer flow
properties than thermoplastics and, as a result, are more difficult to form into
deep thin sections or items with many complex features.
Many thermoplastics can be considered for this application; although glass
fibre reinforcement provides much greater rigidity, improved strength and a
higher heat distortion temperature, these materials are more brittle than the
unfilled ductile polymers and have unsatisfactory impact behaviour for this
application. The high-temperature creep properties of ABS are unsuitable,
and polyamides not only absorb water, which affects properties, but also have
poor dimensional tolerances. The three most suitable materials are therefore
modified PPO, PC and polyacetal (see Chapter 7); a comparison of their
properties indicates that PC is the preferred material. Furthermore, its
transparency helps to ensure that the electrical riders make contact with the
two pick-up rings fixed to the brackets when assembling the unit.
The bracket has been designed with a constant section thickness of 2.5 mm
to ensure that the component has uniform shrinkage and negligible distortion.
It incorporates several radial ribs to provide a rigid and accurate location for
the motor. The toughness of polycarbonate enables two threaded inserts to be
positioned after moulding. Finally, the design incorporates retention lugs for
the electrical cable and features to retain an on-off switch; it also isolates the
electrical parts from the metal wind-up spring.
5 Propylene plastics
Propylene plastics have consistently enjoyed a very rapid growth both

nationally and internationally; there seems to be little indication that they
have reached their limits. The UK usage (Table 5.1) illustrates this growth,
which is founded on the versatility of propylene plastics.
World consumption is divided almost equally between Western Europe,
Japan and America; the total tonnage is exceeded only by polyethylene and
PVc.
The monomer, propylene, is obtained by the thermal cracking of naphtha,
(crude oil light distillate); ethylene, propylene and higher homologues are
separated by fractional distillation at low temperatures. In the early 1950s
Ziegler successfully developed a complex catalyst for the polymerization of
ethylene. Natta applied Ziegler catalysts to propylene and obtained a
'crystalline polymer of high molecular weight. From Natta's discovery in 1954,
it took less than four years to produce development quantities of polypropy-
lene, in spite of the hazards associated with the catalyst and with the handling
of explosive dusts. (Polymer fines are very explosive: a suspension of 1 11m
polypropylene particles in air can be detonated by a 2 mJ electrical discharge.)
5.1 Homopolymer and impact modified grades

The homopolymer has a crystalline melting temperature of 168-170°C; a by-
product is the non-crystallizable variant, atactic polypropylene, (contami-
nated with low-molecular-weight crystalline polymer), which has little
commercial value. This was inevitably isolated in the diluent-based polymeriz-
ation, but recent manufacture, with more discriminating catalysts, seeks to
exploit the whole product. The early polypropylene was of very high
molecular weight and was almost impossible to process; there was even
Table 5.1 Use of propylene plastics

in the UK
Usage
Year (tonnes)
1984 290000
1985 330000
1986 370000
PROPYLENE PLASTICS 73
difficulty in measuring its melt viscosity, which caused a reappraisal of the
Melt Flow Index (MFI) test procedure. The early product was degraded
thermally at 260-280°C to give products which could be processed by
conventional methods. Oxidative degradation was possible at much lower
temperatures, but gave odorous products. Thermal degradation narrowed the
molecular weight distribution, yielding products of good toughness for a given
melt viscosity. However, polymerization followed by degradation, apart from
giving a product with an unacceptable smell, was not attractive economically.
There has been renewed interest recently in the balance of properties achieved
in thermally degraded polypropylene; in particular the compromise between
ease of processing and mechanical properties can be pitched at a different level,
giving both improved productivity and better performance. For fibre applic-
ations these 'controlled rheology' (CR) grades have advantage in lower
spinning temperature for optimum strength. The degradation can be achieved
by mechanical or thermal treatment, y-radiation, oxidation, or by the addition
of peroxides. The last method is the most widely used production technique;
the main characteristic of the CR polymer is a narrowed molecular weight
distribution.
Control of molecular weight at the polymerization stage was achieved by
adding hydrogen as transfer agent, or modifier, but the product has a wide
molecular weight distribution, and is comparatively brittle for its melt
viscosity. Thus, brittleness was a limitation to the development of polypropy-
lene, particularly in mouldings; other problems encountered were oxidation in
processing and use, poor resistance to UV-induced degradation and oxid-
ation, and the development of structure (crystallinity) in the melt if low
temperatures were employed to minimize degradation. Instability was cured
by additives, giving particular fillip to oxidation studies and the development
of new antioxidants. More recently, the use of UV -stable antioxidants has
given PP compounds with still better weathering resistance. The ability to
copolymer r= 0·25 mm
150
E
......
...
2-
()
co
Co
100
.§
B
CD
()
.::: 50
co
t;
.0;
~
0
-40 -20 0 20 40
temperature ("e)
Figure 5.1 Impact properties of propylene plastics r = notch tip radius
process at high temperatures has eliminated problems of melt structure.

The relative brittleness of the homopolymer can be seen in Figure 5.1; the
material, although ductile at 20o e, is embrittled either by a small reduction in
temperature or by a slight increase in the severity of stress concentration. As
with polystyrene, the toughness may be improved in a variety of ways: the
most applicable are discussed below.
(i) Addition of rubber, originally butyl rubber, but now preferably ethylene-
propylene or ethylene-propylene-diene rubber, is an effective method but
necessarily involves a separate processing operation. Such products have
been developed for car steering wheel covers, and for car bumpers
(fenders). The apparently similar procedure of blending with atactic PP
does not give a significant improvement in toughness, since atactic PP is
a very poor rubber, having its glass transition not far below room
temperature.
(ii) Random copolymerization with a second monomer, e.g. ethylene, results in
improved toughness but at the expense of much reduced rigidity, an
inevitable consequence, since the crystallinity is reduced by the inclusion
of the second monomer. The melting temperature is also reduced
significantly, for example, a 97: 3, propylene-ethylene random copolymer
had a melting point of 150°C. Such copolymers are manufactured
commercially and used for film (for bonding to PP textiles, e.g. sacks), for
bottles and for heat-seal coating, applications where the reduced melting
point is not a serious shortcoming and may indeed be an advantage. Film
based on these copolymers is replacing cellophane in the packaging of
cigarettes.
(iii) Block copolymer of propylene and ethylene by sequential polymerization.
This is the generally preferred solution to the problem of brittleness.
Although frequently designated as 'block copolymers', very little block
copolymer is formed in fact, although crystallinity of the two homopoly-
mer species can be detected. The important material, however, appears to
be ethylene-propylene rubber, possibly attached to a polypropylene or
polyethylene chain. The improvement in impact behaviour is achieved
without too serious a deterioration in the rigidity, which is reduced by 10-
15%. The melting temperature is also reduced by a few degrees, compared
with homopolymer (160-165°e compared with 168-170°C).
A substantial proportion of the PP now manufactured is in impact-modified
grades which, in common with the homopolymer, show considerable tendency
of the melt to supercool. This is illustrated in Figure 5.2, where the difference
between the melting temperature, curve (a), and the crystallization tempera-
ture, curve (b), is some 70 o e, even with a cooling rate as low as 16°e min - 1.
The importance of cooling rate can be seen in Table 5.2; the crystallization
temperature for the rates of cooling inherent in commercial shaping processes
is likely to be about 90 o e, unless nucleated grades are used.
~
'c:J
~
(b) cooling
~
:0
!
>
e>
Q)
cQ) (a) heating
c;;
E
a;
-5
80 120 160 200 240
temperature ('C)
Figure 5.2 (a) Heating curve for polypropylene
(b) Cooling curve for polypropylene
0",=2MPa copolymer 0"2

3 0"2= 6 MPa
0"3= 20MPa
OkO~'0~1~0~'~1~~~~1~0~~;::;~~~
time (hr)
Figure 5.3 20°C tensile creep data for propylene plastics
Table 5.2 Crystallization and melting of sequential propylene-ethylene copolymers
Crystallization temperature Melting temperature

(0C) (0C)
Sample cooled CCmin- 1 ) 0.5 5.0 50 0.5 5.0 50
Diluent 119 109 98 161 162 161

Gas phase 124 113 98 164 163 162
Diluent + 0.25% talc 119 162
Polypropylene is reasonably rigid with good creep resistance (Figures 5.3,

5.4). Further, the material has adequate load-bearing capacity for many
applications (relevant data are given in Figure 5.5); the suggested strain limit is
3% (1% for welded components). Although the impact behaviour of the
homopolymer is barely acceptable, that of the modified grades is excellent, as
0", = 2 MPa
3 0"2= 6 MPa
0"3= 20MPa
0·01 0·1 10 10 2 10 3 104

time (hr)
Figure 5.4 60°C tensile creep data for propylene plastics
30
OL-O~·~O-1---0~·1----~--~1~O----1~0-2--~103
time (hr)
Figure 5.5 20 D
e creep rupture and isometric stress data for propylene plastics
illustrated in Figure 5.1. All grades of PP are capable of forming an 'integral

hinge', a thin web of polymer of high strength and durability to flexing.
A particular application, the marine battery lid, is treated in greater detail
below. Propylene-based plastics exhibit the chemical inertness associated with
paraffin hydrocarbons, of which class they are high-molecular-weight mem-
bers; this allows their use in contact with a wide variety of liquids, both
domestic and industrial. In view of their structure, propylene polymers have
excellent electrical properties, including very low dielectric losses.
On unusual feature of the structure-properties relationship is the existence
of a number of crystalline forms of PP. This might have remained a scientific
curiosity, except that some dyestuffs used for colouring the plastic nucleate the
unusual crystalline form, the [3-form, which is associated with type III
spherulites, and inferior mechanical properties. Some batches of PP, parti-
cularly propylene-ethylene sequential copolymers, have a propensity to form
Figure 5.6 Micrograph showing an unusually high concentration of Type III spherulites. Scale
bar lOOjlm
type III spherulites; gas-phase polymers sometimes show a surprising

concentration of these species (see Figure 5.6). It may be more than
coincidence that such products appear to be relatively brittle. This form is also
favoured by shear during crystallization, and thus may occur during welding.
Polypropylene has for many years been used for car battery cases, because
of its light weight, high impact strength, chemical resistance and fast moulding
capabilities compared with other plastics. It is no surprise that lids for such
batteries should also be made from PP. AB Tudor (Sweden), however, designed
other functions into the lid. Marine batteries are frequently carried between
ship and shore and, therefore, require handles. An immediate solution would
be to fit two 'clip-on' handles to the lid, which would be completed by fitting
another moulding to seal the filler holes for each cell. The component would be
fabricated from several parts; however, real economies would result from
making the lid of a single moulding, incorporating integral hinges. In the final
design, two integral hinges are employed for each of the two carrying handles
(Figure 5.7a). When folded down, each handle presents a flat upper surface,
flush with the filler caps and is retained in that position by snap-fitting two
square hollow projections on the handle over circular studs moulded in the
base of the lid. A further function of the handles is to cover the terminals when
in the closed position. In the raised position, the handles are brought together
and the weight of the battery is shared between the four hinges. Furthermore,
at each end ofthe lid is a flap bearing three filler caps, and integrally hinged to
the lid. When the flaps are in the closed position, each cap seals the aperture for
its cell (Figure 5.7b). Integral hinges can be injection moulded, heat formed or
Figure 5.7(a) Impact-modified PP marine battery case; carrying handles in use
Figure 5.7(b) Impact-modified PP marine battery case: cell cap seals. The case of the Tudor
marine battery is injection moulded by Boras Konstahts AB (Sweden) and the lid by Norsk
Teknisk Parsalens AB (Norway). (a) and (b) by courtesy of leI Ltd.
Figure 5.8 Container formed of two blow-moulded parts joined together by integral hinge. By
permission of RB Blowmoulders Ltd.
machined; they derive their strength from the molecular orientation which is
initiated during the moulding process, and completed by subsequent flexing of
the hinge. The normal range of hinge thickness is from 0.25 to 0.6 mm,
depending on the stiffness of operation and the strength or tear resistance
required.
Another application exploiting an integral hinge is shown in Figure 5.8,
which is a central fitting for Ford heavy lorries: the two halves of the container
are blow-moulded simultaneously with the formation of the integral hinge.
The pattern of usage of polypropylene is dictated by the physical and
chemical properties and by price, particularly the price in relation to
competitive materials and processes. Both the homopolymer and modified
variants are available in grades to suit a wide range of conventional shaping
processes; in addition, special grades have been developed for novel processes,
such as the 'solid-phase pressure-forming process' for shaping PP into thin-
walled containers at temperatures which, although elevated, are below the
melting temperature of polypropylene. This overcomes the problem of
inadequate melt rigidity, which restricts conventional thermoforming.
The properties detailed above lead to the following main areas of
application.
(i) Homopolymer: biaxially oriented film and unoriented cast film for
packaging and electrical capacitors etc; uniaxially oriented film and
fibrillated film for carpet-backing, sacks, twines, ropes etc; uniaxially
oriented strapping tapes; spun fibres; injection-moulded measuring
cylinder for photographic chemicals; blow-moulded bottles and
containers.
(ii) Impact-modified grades: injection mouldings, e.g. bottle crates, tote boxes;
chairs; pipes; liquid storage tanks, etc. The particular cases of a car coolant
reservoir tank (Figure 5.9) and a chair shell (Figure 5.10), exemplify uses of
these materials.
Car radiator reservoir tanks are now made in propylene plastics, because
they offer advantages over metal in design flexibility, light weight and no
corrosion. The containers are blow-moulded for the speedy production of
large quantities, as opposed to rotational casting, and complicated shapes can
easily be moulded (Figure 5.9). Service requirements are to withstand under-
bonnet temperatures; to be resistant to anti-freeze and brake fluids; the
translucency, enabling the coolant level to be seen, is an added advantage.
Heat-stabilized, impact modified PP satisfies the performance criteria, and
provides a tough and robust part. However, blow-moulding is limited in the
number of inlets/outlets possible; frequently, additional outlets are added by
heat-welding. The filler necks are injection-moulded in glass fibre-reinforced
PP to provide a more rigid section to locate the traditional radiator cap. The
manufacture of these tanks has seen a number of variants of shaping
techniques and materials. Some are injection-moulded/heat-welded compo-
Figure 5.9 Coolant expansion tank for Jaguar car, blow-moulded in propylene-ethylene
sequential copolymer. By permission of RB B1owmoulders Ltd.
Figure 5.10 Pel stacking chair moulded in impact-modified PP

nents in natural or glass-fibre-reinforced PP. Unfortunately, injection-

moulding demands an easier flow grade of polymer compared with blow-
moulding (or mouldings with high residual strain are produced, and this
unfavourably affects the compromise between processing and environmental
stress cracking). Ethylene glycol, the main ingredient of anti-freeze, is a
significant cracking agent for PP; the position is exacerbated further by the
large area of welding, which is usually far from perfectly carried out.
The design of chairs is continually scrutinized; the result has been a
multitude of chair designs utilizing most of the commodity plastics. Many of
the designs were for specialist uses, and have been of little commercial
significance. However, since the 1930s there has been a market for low-priced
seating for canteens, assembly halls and general use. This market required that
these chairs could be stacked together to be stored compactly, and was
obviously influenced by the large market for mass-produced chairs, and the
commercial importance of this type of chair (Figure 5.10).
The major factors in the specification required the chair to contain a main
structural element to support the back-rest and the seat; the material should be
sufficiently flexible to be comfortable in use and the product must be
attractively priced. The two most appropriate materials are high-density
polyethylene (see Chapter 6) and polypropylene. HDPE has better low-
temperature impact properties which could be an advantage for external
seating in cold climates. However, when PP was subjected to an accelerated
user test to simulate the load exerted by a 100-kg person pressing backwards
on the chair for 100000 cycles, the seat retained a permanent set of only
3.17 mm at the top of the backrest. This convinced the designers that impact-
modified PP was suitable as a chair shell, as well as possessing superior creep
properties to high-density polyethylene. A special grade of copolymer was
chosen which possessed good flow characteristics, rigidity, gloss and good
impact properties. An antistatic additive was also incorporated to reduce the
amount of dust attraction and most recently, the fire retardancy has been
improved markedly.
Comment has already been made of the use of PP which has been toughened
with rubber, usually EPDM, in applications such as car bumpers (fenders).
The application of surface coatings to modified PP mouldings used as external
components on cars, e.g. front spoilers, is problematic, especially with long-
term interfacial bonding. The theme of employing propylene polymers as
reinforcing agents in a variety of rubbers, including thermoplastic elastomers,
is being exploited increasingly. Additional advantages accrue from cross-
linking the rubber in the presence ofPP, when undoubtedly some interlinking
occurs, which stabilizes the dispersion of PP and the rubber. These materials,
exemplified by Santoprene™ (Monsanto) and Kraton G™ (Shell Inter-
national), are penetrating markets such as seals and gaskets, in addition to
being already accepted in shoe components.
5.2 Filled polypropylene
One ofthe main application deficiencies of PP is its inadequate rigidity, whilst
the high mould shrinkage is frequently a problem in processing. Both features
can be improved by the use of composites (blends ofPP with fillers), which may
also reduce the price ofthe material. Composites involving the addition of up
to 30% calcium carbonate have been used for wastepaper baskets, where the
increased rigidity is required in a cheapened product and the reduced strength
is not a serious problem. For more exacting applications, structured fillers
such as talc, mica and asbestos, are used, the first being widely and increasingly
employed (data are given in Table 5.3).
A typical application for talc-filled PP is heater boxes for many cars and
trucks, the use of this particular material allowing injection moulding of a
complex shape of adequate stiffness, and with softening behaviour which
allows its use under the bonnet. Traditionally, heater boxes were fabricated
using phenolic cross-linked plastics; now they are made from thermoplastics,
because of the design freedom and the ease of manufacture of complex parts.
Unfilled PP suffers from poor dimensional tolerance and warping, and is
considerably affected by temperature; on the other hand, talc-filled polypropy-
lene has superior after-moulding tolerances and less warpage, because the filler
reduces the mould shrinkage. Talc-filled grades are recommended for
applications demanding better dimensional stability, higher rigidity and
improved heat deflection temperature, and cheapness. However, the addition
of talc is detrimental to other properties, the impact strength is reduced, the
flow length is reduced and the specific gravity is increased. This example of a
heater box is a complex moulding: several side cores are used to form features
which are not parallel to the direction of mould opening. Talc-filling also
reduces sinkage on the surface of the moulding, enabling thick sections to be
joined, with only a faint trace of a sink mark. A heater box is illustrated in
Figure 5.11.
For the best reinforcement, glass fibres are used, but it is essential to provide
a good bond between reinforcement and matrix; composites involving carbon
fibres are of little commercial interest for PP. Relevant design data for glass-
fibre-reinforced PP are given in Figure 5.5. Examples of the use of glass-
reinforced PP include air filters, lamp housings and the filler neck of car
coolant-reservoir tanks. Some coolant reservoir tanks have been manu-
Table 5.3 Properties of talc-filled polypropylene
40% Talc-filled
Property Unfilled copolymer copolymer
Flexural modulus (GPa) 1.38 3.55

Izod Impact (Jim) 133 48
Figure 5.11 Heater box from a Ford vehicle
factured in glass-reinforced PP, although ethylene glycol at high temperatures

is not the most sympathetic treatment for the comparatively low-molecular-
weight polymer inherent in reinforced grades. In the design of components in
glass-fibre-filled PP, it should be remembered that injection-moulding will
induce orientation in the direction offlow, to the detriment of properties in the
transverse direction.
5.3 Foamed polypropylene

Another way of improving the economics of polypropylene usage is in foams;
structural foam applications are of increasing importance, and agricultural
produce containers of half-tonne capacity are already in use. Foams are being
used in place of solid mouldings to give enhanced stiffness and greater
economy: an example is the handle of a light-duty chain-saw where rigidity,
strength, attractive finish and economy are important. Reinforcing fillers may
be incorporated in the foam; one of the largest mouldings based on glass-
reinforced PP is the static drum of the Philips washing machine. The modern
unit comprises few major parts, one of which is the tank, which is used to locate
the rotating drum and the motor, as well as inlet and outlet pipes, suspension
Figure 5.12 Philips washing machine tanks-(left) vitreous enamelled steel and (right) coupled
glass-reinforced structural foam PP, moulded by Cabinet Industries Ltd., Alfreton. Photograph
by courtesy of ICI Ltd.
springs, balance weights and damper mountings. In the past, front-loading

machines contained vitreous enamelled steel tanks, which are very expensive
(Figure 5.12a). The advantages that plastics immediately offer are good
corrosion resistance, even to the most aggressive detergents, and low cost,
since the component can be made easily in one injection moulding. The only
doubts about this product were the strength and stiffness of the plastics
materials, and in the very high tool costs incurred for moulds with several
sliding cores and of large size. The material chosen was coupled glass-
reinforced structural foam PP, since it has good chemical resistance, and the
glass fibres increase the modulus. Foaming enables the product to adopt rigid
thick sections which are dimensionally consistent, and the component will
withstand thick and thin sections without undue distortion (Figure 5.12).
Foaming is produced by physical or chemical blowing agents, or by
introducing nitrogen gas into the melt at the nozzle at the time of injection.
Whichever method is adopted, when the melt is injected into the cavity, the
material foams, expands and fills the cavity. The melt forms a solid skin which
has been in contact with the mould surface and has solidified, giving an outer
solid skin and an inner foamed core. The skin/core ratio depends on the
thickness of the moulding, and the density of the core depends on the amount
of material injected into the cavity. In structural applications it is not advisable
to use a core density of less than 700 kg m - 3 for unfilled polypropylene, and
the wall thickness should be not less than 6 mm, otherwise no foaming will
occur.
The advantage of a foamed structure arises when a part is subjected to
flexural loading, for which case the stiffness is proportional to the cube of the
depth of the beam. A further useful feature of foaming, compellingly

demonstrated by the hull of the Topper sailing dinghy, is that mouldings of
large area can be made without the need to employ impossibly large locking or
clamping forces. The huge amount of melt for this moulding (20 kg) requires
that two injection presses feed the mould in parallel, but the locking force for
the two mouldings for the hull (of total projected area 3.5 m 2) is only 3200
tonnes and is entirely feasible. The absence of sink marks in this largest
injection moulding in commercial production is an added advantage:
unreinforced impact-modified PP is the basis for this foamed structure.
Another way of creating a foam is to incorporate hollow sphere fillers; such
composites, known as syntactic foams, have a superior surface finish
compared with conventional foams. Flammability can be reduced by
additives, e.g. antimony trioxide plus chlorinated waxes; such additives, while
retarding the ignition, lead to increased smoke emission. The flammability of
PP is a hazard restricting its widespread use in the interior of buildings.
5.4 Miscellaneous applications of propylene polymers

Typical of new applications in the packaging field is an extruded card
substitute based on talc-filled sequential copolymer which can be extruded
and cut, creased, folded and glued like cartonboard, and which handles well on
high-speed carton-making machines. Alternatively, it can be thermoformed.
The product is capable of withstanding deep-freeze conditions, is free from
water absorption and is resistant to oils and greases. It is ideally suited as a
container for microwave oven usage and, as it is inherently stronger than
carton board, thinner sheets can be employed.
Corrugated sheet extruded directly from polymer is a strong competitor
to corrugated board on cost and particularly on technical performance; the
new product is lighter in weight and is unaffected by water, oils and solvents.
Oriented blow-moulding technology has been applied to polypropylene
bottles: through biaxial orientation, PP bottles gain significantly in clarity, as
well as in rigidity, permitting thinner walls. Another advantage for PP bottles
is the high heat distortion temperature, which allows the container to be
capped after hot-filling.
Although electroplating grades ofPP are available, the important develop-
ment in plating appears to be a pretreatment process which eliminates the need
for special grades. It has the further advantage of requiring fewer steps than
other methods, and hence is low in cost. A reactive chemical is used to swell the
surface of the PP; evaporation of the solvent leaves the reactive chemical
trapped in the surface, which is then brought into contact with an aqueous salt
solution, making the surface electrically conductive. The pretreated surface
can then be plated by standard methods. As well as operating at lower
temperatures, chromic acid and expensive palladium chemicals are not used,
making the new pretreatment very competitive with alternative methods.
6 Other polyolefi n plastics
In addition to propylene polymers, the following polyolefins are produced

commercially.
(1) Polyethylene
(i) High-density (HDPE), produced by comparatively low-pressure
routes with Ziegler or complex oxide catalyst
(ii) Low-density (LDPE), traditionally made by a high-pressure route
(iii) Linear low-density (LLDPE), comparable in structure and
general properties with LDPE and manufactured by copoly-
merizing ethylene with butene, hexene, octene or 4-methyl pentene at
low pressure
(iv) Very low-density (VLDPE) is an extreme version of LLDPE
(v) Ethylene copolymers, typically with polar monomers such as vinyl
acetate, are made by LDPE technology
(vi) Blends of various types of ethylene polymers are now widely used;
sometimes their use is deliberate, sometimes incidental.
(2) Polybutene
This is an isotactic polymer, produced by Ziegler-Natta catalyst by a
process analogous to that used to manufacture polypropylene.
(3) Poly( 4-methyl pentene)

Another isotactic polymer produced by Ziegler-Natta catalyst.
6.1 Polyethylene
Chronologically, the manufacture ofLDPE preceded that ofHDPE, but since
the latter has the simpler structure it will be considered first. The monomer,
ethylene, was originally obtained from sugar by fermentation and
dehydration:
molasses ~ ethyl alcohol ~ ethylene
Ethylene is now obtained from oil, or preferably light naphtha, by cracking.
6.1.1 High-density polyethylene

Two distinct processes were developed almost simultaneously in the mid-
1950s, based on Ziegler catalysts and on mixed oxide catalysts: the Phillips
process is the most widely employed of the latter.
Ziegler and Phillips HDPEs can be virtually unbranched hydrocarbon
chains, leading to densities in the range 0.945-0.965 Mg m - 3, although
commercial Ziegler polyethylene can have a few ethyl side-groups, (5-7 per
1000 chain atoms). Oxide-catalysed polymers generally have the highest
densities of the polyethylene series.
Processing is dominated by the linearity of the chains, leading to pronoun-
ced flow orientation and a rapid crystallization rate with only little supercool-
ing compared with polypropylene. The attainable crystallinity in standard
processing operations is somewhat higher than for PP, resulting in generally
higher shrinkage. For reasons concerned with processing, HDPE is sometimes
preferred to PP for small injection mouldings, where orientation is not a
problem, or where it can be tolerated (margarine tubs), and for very large
blow-mouldings, where the stability of the parison is helped by the orientation
induced during extrusion, and by the pronounced non-Newtonian behaviour
of the melt.
The properties of HD PE include a crystalline melting point lower than that
of PP, 130-135°C, with very little supercooling and a rapid crystallization
rate. HDPE is comparable in rigidity with PP, but with inferior creep
behaviour and scratch resistance. Figure 6.1 shows flexural creep modulus as a
function of time and the considerable effect of temperature on the deformation
behaviour. The effect of density is seen in Figure 6.2, which embraces data
covering a density range including LDPE and HDPE. Low-viscosity grades of
HDPE are brittle if pronounced stress concentrations are present, but high-
molecular-weight materials are tough, even at low temperatures. Low-
molecular-weight polymers may stress crack in the presence of some
::J
"0
o
E
c. 25'C
C1>
C1>
t;
oOL·O~1--~O~'1~--~--~10~--~10~2~-710~3~
log time (hr)
Figure 6.1 Flexural creep modulus as a function of time for HDPE (density 0.953 Mg/m3) for
stress of 4 MPa
OTHER POL YOLEFIN PLASTICS 89
1·5
~ 1·0
::J
"0
o
E
g.
(I)
0·5
U
~
'iii
r::
~ 0'~9~1......--o....9-3-"----:o:-'.9~5~--~0·.."9.,,,.7--'-
density (Mg/m 3 )
Figure 6.2 Dependence of IOO-sec tensile creep modulus at 1% strain on density of polyethylene
chemicals. Density is some 5% greater than PP, with implications for volume
cost. HDPE is flammable, although flame retardants improve the polymer in
this respect.
As noted above, HDPE is very important for blow-moulding, especially
large-capacity containers, such as 220-litre barrels and water butts; dustbins
are shaped in this way, two at a time. HDPE is also important for bleach and
detergent bottles where the higher rigidity compared with LDPE leads to a
cheaper package. Blow-moulding technology is exemplified by a prestigious
application of growing importance~fuel tanks for road vehicles. A particular-
ly detailed study has been made of the Peugeot 309 tank (Figure 6.3) which has
a mass of 6.5-7.5 kg, a capacity of 481itres and is produced in a relatively high-
molecular-weight HDPE (i.e. the MFI at 2.16 kg at 190°C using a standard die
is 0.1 g per 10 min). The requirements, apart from the obvious one of being able
to shape the container, include high strength and toughness at - 40°C and low
permeability to fuel~a loss limit of 20 g per 24 h at 50°C is specified. HDPE,
because of its high crystallinity, meets the need for an effective barrier at a
mean thickness of 5.5 mm, while the impact requirement specified by the EEC
is satisfied by the grades of HDPE developed for this application. As the
thickness is 5.5 mm, the moulding cycle is dominated by the cooling time. An
increase in productivity can be achieved most readily by reducing the cooling
time by providing internal cooling in addition to the normal heat transfer
route via the mould. Two aspects are important: increase in the heat transfer
coefficient, plastic to air, by circulating the air and provision of sufficient
capacity to extract the heat energy. The latter again comprises two factors, the
volume of coolant and the temperature at which it is introduced [1].
Reference has been made to injection moulding, which is a fair market for
HDPE. Extruded pipe from HDPE and a tougher variant of lower density is
widely used for natural gas distribution, particularly in cold climates where
some failures of PVC (Chapter 8) have been encountered. HDPE has also been
formed into mudguards for commercial vehicles, where the non-corroding
Figure 6.3 Fuel tank for Peugeot 309, blow moulded in HDPE. By permission of RB
Blowmoulders Ltd.
polymer withstands the arduous service conditions. Very thin film, made by
the tubular process, finds application as a tissue-paper replacement and for
point-of-sale wrapping, especially of wet foodstuffs, such as meat and fish.
HDPE has been preferred over PP in milk-bottle crates, since creep is less
important than for beer crates and the incidence of impact abuse at low
temperature is likely to be greater, but the trend is to PP because of its more
tolerant moulding characteristics.
HDPE, and more recently, modified polyethylene oflower density, are used
in gas distribution systems for many important reasons, including economic
shaping, ability to withstand both the internal and external loads, good low-
temperature impact properties and relative impermeability to the gases
10
co
a.. 8
2 7
!/)
!/)
6
~
t) 5
~ 4
:::l
C.
;: 3
2
10 3 10 5 10 7 10 9
time (5)
Figure 6.4 Rupture stress vs. time for HDPE pipe at various temperatures
carried. Gas pipes are required to have many years of maintenance-free life, so
it is important for the design of the system to be correct. A typical installation
requires the pipe to operate for up to 50 years at 20°C at an internal pressure of
0.25 MPa, with a mean diameter of 250mm. For thin-walled pipes the wall
thickness can be calculated, based on a failure stress after 50 years of 6.5 MPa
(Figure 6.4). The safety factor suggested in BS 3796 is 1.3; hence the design
stress is 6.5/1.3 = 5 MPa and the wall thickness required is 5 mm.
This calculation applies for an ideal pipe, shaped under perfect conditions
and tested in a laboratory. However, imperfections may be generated during
extrusion or in handling and installation. Gas engineers are anxious to avoid
failure caused by a longitudinal crack propagating through the wall and
unzipping several kilometres of pipe. A fracture mechanics approach is
required, based on a fracture toughness of 3 MN m - 3/2, which has been
determined in laboratory tests on this material. The crack will propagate if the
rate of energy release resulting from the growth of the crack exceeds the
fracture toughness, thus imposing a limiting diameter on the pipe, or a limiting
hoop stress (internal pressure), to which the pipe can be subjected. All pipes of
diameter less than the critical should be incapable of catastrophic crack
growth, or of creep rupture when operated at the specified pressure rating.
However, pipes of larger diameter must be operated at a pressure lower than
that corresponding to the creep rupture design stress if runaway cracks are to
be avoided.
As with polypropylene, reinforcement of HDPE with short glass fibres is
practised; compounds with loadings of glass up to 20% are available, giving
much improved rigidity and reduced thermal expansion compared with the
unreinforced material. The modulus is increased by a factor of 3 for 20% glass
fibre but, in the presumed absence of coupling of the glass to the matrix HDPE,
the stress at yield IS unchanged and may even be reduced in some

circumstances.
6.1.2 Low-density polyethylene

Low-density polyethylene, generally considered to have a specific gravity in
the range 0.915-0.930, is manufactured at high pressure and high temperature,
usually 1500-3000 bars at 150-250°C, in a process which is usually
continuous in stirred reactors or tubes. The reaction conditions invite free
radical attack on polymer, leading to long-chain branching and to pendant C 2
and C4 chains, and to other irregularities, including un saturation. Molecular
weight, molecular-weight distribution and branching are controlled in the
reaction by modifiers, by temperature and pressure, and by the type and
concentration of initiator.
The structure of LDPE is generally similar to that of HDPE, but the
crystallinity is limited by branches which cannot fit into the crystalline lattice.
Crystallinity is frequently 50-65%, is also dependent on molecular weight, the
higher-molecular-weight grades achieving lower crystallinity. Branching is
specified as the number of CH 3 per 1000 carbon atoms, generally 25-30 for
high pressure polymers. Specific gravities of the crystalline and amorphous
states are very different, 1.01 and 0.84 respectively, giving a method for
assessing crystallinity: X-ray methods are also used. Melt Flow Index (MFI), is
still widely used as a monitor of processability: the higher the MFI the greater
the fluidity (the lower the viscosity), of the melt. Grades of LDPE suitable for
all processing methods, including rotational moulding, are generally available.
Notes on the processing methods employed are given in the survey of
applications below.
The properties of LDPE are those expected of a lower-crystallinity variant
of HDPE; the melting point is lower, approximately 115°C, varying with
density, (Figure 6.5), with a more gradual melting process. It is almost a factor
~ 120
E
'0
0-
.,.
Ol
.c:
Qi
E 115
CI)
c:
c;;
~'-'
110~~____~____~~~__~~
0·915
density (Mg/m3)
Figure 6.5 Dependence of crystalline melting point of LDPE on density

--
N
cg E
.,......E
III
--
Q. Q.
~
~ (d) ~ .5.
"
..
~
.J:.
c01 __
00';'
.2
::J
2000~
.J:.
I!?..c
1ij~ 20
"
00 E
0
1500 ~
C,
QI . . c. 1ij
==01
III c:
QI
QI ....u
c: t; co
.. "
QI
!l ~ 10
QlIII OO~ 1000.§
III
111- c:
~
E·~ !l 'iii
E>- 0 c:
00'; 500 !l
::J 0.915 0·92 0·925 0·93 0
density (Mg/m3)
Figure 6.6 Effect of density of LPDE (MFI = 0.25 gjlO min) on some mechanical properties
of 10 less rigid than HDPE or polypropylene and the yield stress is much
lower. Both modulus and yield stress depend on density (crystallinity) and on
MFI (Figure 6.6,6.7). At moderate and high molecular weights the polymer is
very tough, but low-molecular-weight grades are susceptible to environmental
stress cracking. Long-chain branching affects molecular weight vs. processing
behaviour favourably. Electrical properties can be excellent, but depend on
impurities and additives. Additives are frequently incorporated in LDPE to
modify the properties for particular applications; these include flame retard-
ants, slip and anti-blocking additives for film, antioxidants, UV stabilizers,
pigments and occasionally prodegradants.
Applications include film for packaging manufactured by the tube-blowing
process, which consumes some 70% ofLDPE production; a miscellany of uses
takes the remaining 30%, including:
N
E
.,......E
.5. U
1500 ~
C,
c:
§
QI
1000
u
co
C.
.S
~
'iii
c:
o ~____'--___----"~__""" 0 !l
0·1 10
melt index (MFI190·C, 2·16 kg)
Figure 6.7 Effect of Melt Flow Index of LDPE (density 0.918 Mgjm 3 ) on some mechanical
properties
Bottles Extrusion blow moulding

Mustard jars Injection blow moulding
Bowls, buckets Injection moulding
Cold water tanks Rotational moulding
Paper coating Extrusion.
For many years, wheelbarrows have been made from wood or metal, both of
which have to be protected from the degrading effect of weathering.
Unfortunately, the conventional protective coatings are not durable and the
substrate is quickly exposed to the elements. The idea of using a plastic
moulded bin as part of a wheelbarrow was novel, and allowed changes in the
general design. The bin is injection-moulded, so that there is little hindrance to
introducing more complex shapes: the design of the barrow was changed so
that it was much deeper, with a less acute tipping angle, enabling a larger
volume of material to be carried. The feet were connected to the base and the
handles placed wide apart to make the wheelbarrow more stable in use. The
main performance requirement was that it should withstand the load when
full; it should also be durable enough to withstand the impact of objects such
as bricks being thrown into it from a short distance. Assuming a maximum
load of 150 kg, the approximate stress, assuming a wall thickness of 3 mm, is
less than 1 MPa, a stress level which could be tolerated by all thermoplastics:
the choice depended, therefore, on impact performance and price.
Low-density polyethylene is still one of the cheapest thermoplastics,
possesses excellent impact performance, but is very flexible. A grade of LDPE
was selected to give the best overall properties, viz. a density of 0.92 Mg m -3
and MFI of 12~14g per 10 min (2.16kg at 190 C). D
6.1.3 Linear low-density polyethylene

As noted at the beginning of this chapter, the structure and properties of
LLDPE are comparable with those of LDPE, with the notable difference that
LLDPE does not have long-chain branching. The practical consequence is
that LLDPE has much superior strain accommodation, which allows far
greater draw-down, both in the melt and in the solid state. It is interesting to
compare the tensile stress vs. strain curves for HDPE, LDPE and LLDPE (see
Figure 6.8).
The LDPE and LLDPE are of similar density and show very similar
behaviour up to yield, with the HDPE having, as expected, a much higher yield
stress, fully supporting the thesis that the behaviour to yield is dependent on
the crystallinity. However, molecular topography takes over in the later stages
of the test. The elongation of LDPE is limited by long-chain branching, and
that of HDPE by shortage of amorphous polymer. Not being limited by these
two factors, LLDPE can extend to very high elongation.
30
LLDP
C
0...
~
20
(f)
(f)
w 10
0::
I-
(f)
200 400 600 800 1000 1200 1400
STRAIN (%)
Figure 6.8 Tensile stress vs. strain curves for various polyethylenes
The melt rheology of LLDPE differs from that of LDPE, so that processing
equipment for the latter cannot be used without modification. Consequently,
much interest in blends has been generated; these are discussed later in this
chapter.
Film appears to be the main application area at present.
6.1.4 Very-law-density polyethylene

This material, with a density down to 0.88 Mg m - 3, is believed to be a
copolymer of ethylene with a higher olefin. No pattern of applications seems to
have been established.
6.1.5 Blends of ethylene polymers

It might seem axiomatic that the various polymers of ethylene discussed above
should be miscible; indeed, recently it was recommended that blends ofHDPE
and LDPE be used to obtain properties intermediate between those of the
homopolymers. However, work in several centres has shown that miscibility is
the exception rather than the rule: even blends of LDPE and LLDPE tend to
become 'unmixed' into separate crystalline phases. This sounds a warning
concerning masterbatch carrier polymers; it is not prudent to use a LDPE or,
worse, an EV AC copolymer as carrier in a masterbatch introduced into
matrices ofHDPE and LLDPE, or, worse, polypropylene. It may apparently
------LOPE
o
x
UJ
~"O_
~
HOPE
o
D
Z
UJ
50 70 90 110 130 150
TEMPERATURE (OC)
Figure 6.9 Thermograms of LDPE, HDPE and a 50/50 blend of the two
a LOPE (I.t HEATING)
LOPE (2nd HEATING)

b - -__
~O:Y.LO/SO"LLOPE
(I.t HEATING)
o c
x
w 50"LO/SO:Y.LLOPE
d - - - - ( 2 n d HEATING)
- - - LLOPE (I.t HEATING)

e
f _ _ _ __ ----LLOPE (2nd HEATING)
o
o
z
w
II II
40 60 80 100 120 140 160
TEMPERATURE (DC)
Figure 6.10 Thermograms of LDPE, LLDPE and a 50/50 blend: quenched and slow-cooled
specimens
OTHER POLYOLEFIN PLASTICS 97
-- --- --- ----

12
!50" c IoIOU..D
0
a.. 10 -
~
zo" C IoIOU..D
0 8
..J
UJ
>- 6
I-
<
Ul 4
Ul
UJ
a::
I-
Ul 2
0
0 20 40 60 80 100
LLDPE (% )
Figure 6.11 Yield stress vs. composition for LDPE-LLDPE blends. (Specimens did not reach
yield in the flow direction)
30 II:) zo "c IoIOU..D
0
a..
~
UJ
a:: 20
::>
..J
<
1L.. 15
I-
<
Ul 10
Ul
UJ
a::
I- 5
Ul
0
0 20 40 60 80 100
LLDPE (%)
Figure 6.12 Failure stress vs. composition for LDPE-LLDPE blends
100l!: LLllPE
~
a
70l!: LLO/30l!: HO
b
0
X SOl!: LLO/SO"/. HO
W c
30l!: LLOnQll: HO
d
e 100l!: HOPE
0
0
Z
W
4-0 50 80 100 120 14-0 150 180
TEMPERATURE (oe)
Figure 6.13 Thermograms of LLDPE, HDPE and blends
30
25
"
CL
:::<
(f)
20
(f) x
W x
a: 15
f-
(f)
W
..J 10
(f)
Z
W
f- 5
a
0 HOPE 30 50 70 100 HOPE
100 LLOPE 70 50 30 a LLOPE
BLEND (xl
Figure 6.14 Yield and failure stresses for LLDPE, HDPE and blends
be tolerated in a large number of cases, but critical applications may fail. The
separation is shown in differential scanning calorimetry thermograms: blends
of LDPE -HDPE are shown in Figure 6.9, and of LDPE-LLDPE in
Figure 6.10. The difference between Figure 6.10 (c) and (d) is that (c) was
quenched from the melt, whereas Figure (d) refers to slower cooling. Clearly,
for the LDPE-LLDPE system the response is very dependent on the thermal
history, and it is no surprise that the mechanical properties are affected.
However, the yield stress in the transverse direction seems to be little
affected by the mould temperature (Figure 6.11), with the data being in the
order expected, i.e. the quenched samples having the lower yield stresses. A
similar picture is presented for the breaking stresses in the transverse direction
(Figure 6.12); however, a very different situation obtains in the flow direction,
(machine direction), where we find that the considerably higher failure stress is
associated with the more rapidly cooled samples. The difference is appreciable,
some 15%.
By contrast, the LLDPE-HDPE system appears to be miscible and co-
crystalline over the entire composition range; Figure 6.13 shows a steady
increase in melting temperature as the HDPE content is increased.
The mechanical properties are generally as expected (Figure 6.14), with the
yield stress increasing monotonically with HDPE content, while the breaking
Figure 6.15 Cross-linked micro cellular moulded tyre (EVA) on polypropylene wheel for child's
push-chair (Andrews-McLaren "Baby Buggy")
stress is sensibly constant, although the value for HDPE seems to be a little
lower than the remainder.
6.2 Ethylene copolymers

Ethylene copolymerized with other olefins has already been covered above.
Ethylene copolymers with polar comonomers are made by the high-pressure
route; the favoured monomer is vinyl acetate (V AC) which, under the usual
reaction conditions, copolymerizes with ethylene ideally. Small amounts of
VAC reduce crystallinity and melting point, but increase toughness and
flexibility: such copolymers (EV AC) are used for tough film, although the
moisture permeability is increased by the inclusion of the polar groups.
EVAC was chosen for beer pipes since it is sufficiently flexible, is harmless in
direct contact with foodstuffs, and does not taint the beer.
High-molecular-weight copolymers of higher VAC content (20-40%) find a
variety of uses as thermoplastic rubbers, particularly as microcellular soling
for shoes and as moulded, cross-linked, foamed tyres for the Andrews-
McLaren Baby Buggy™ (Figure 6.15). Low-molecular-weight grades are used
as reinforcing additives for wax coatings, hot melt adhesives, etc.
Ionomer resins are ethylene copolymers with an active functional group in
the comonomer, frequently carboxyl. This is 'neutralized' with metal oxide to
give a tough thermoplastic rubber.
6.3 Polybut-l-ene
Up to 1957, only the non-crystallizable (atactic) low-molecular-weight
polymer was known; this is still used as a viscosity-stabilizing additive for oils.
Isotactic, crystalline polymer is generally similar to PP, but the melting point
is some 40°C lower. It is manufactured by a process similar to that for
polypropylene.
Polybutene is unusual in that there are two crystalline forms, I and II; the
latter is metastable but is always formed from the melt during normal
processing. The transition from II to I occurs at room temperature over 2-5
days, with increase in density, and consequent change in dimensions.
Processing and properties are very similar to those of PP, except that the
melting point is 130°C (for Type I crystallinity); similarly, the glass transition
temperature is some 20°C lower than PP. Polybutene is slightly less rigid than
PP, but has a significantly better creep resistance and seems to be immune to
environmental stress cracking.
Applications must be tolerant of the crystal transition and benefit from the
creep behaviour. Pipes, especially for high-pressure distribution, appear to be
the only important outlet, particularly for cold water and gas, and for hot
water installations. They are manufactured in diameters up to 460 mm,
principally in North America. Polybutene is also abrasion-resistant and finds
application for the transportation of aqueous mineral slurries, e.g. gypsum, by
pipeline.
6.4 Poly-4-methylpent-l-ene (P4MP)

This polymer has the repeat unit:
The isotactic form is the only polymer of commercial importance. An

unusual feature is that bulk polymer is transparent because the molecular
chain is only very slightly birefringent. A second unusual feature is that the
crystalline density and the amorphous density are very similar. The transpa-
rency is further enhanced by nucleation giving finer texture, and by balancing
crystalline and amorphous densities even more closely, by copolymerization.
The monomer is obtained by the dimerization of propylene.
The principal properties of poly-4-methylpentene are a melting temperature
of 230-235°C and glass transition 40-50°C. There is some tendency to
brittleness, although P4MP is tougher than glass, but is very susceptible to UV
attack. It is the only bulk transparent polyolefin in commercial production or
development. The high melting point forces processing temperatures into the
degradation range for the polymer. Melt stabilizers and lubricants are
employed; even so, it is difficult to mould orientation-free products, and the
presence of residual stresses increases the probability of brittle failure at low
imposed stresses.
Applications include a number of small items which require polyolefin
inertness, reasonable toughness compared with glass, coupled with either
transparency or high softening temperature. Examples are: spirits dispensers,
automatic milking equipment, car interior light covers and 'cook-in-the-bag'
trays. P4MP is an expensive material, but has a low specific gravity, 0.83,
making it cheaper on a volume basis than its main competitor, polycarbonate,
which is also more susceptible to chemical attack. P4MP can withstand up to
50 'hot air' sterilization cycles of 1 h at 160°C, as recommended by the British
Medical Research Council. However, its brittleness makes it unsuitable for
many applications; it has only slightly better impact properties than PMMA.
Another drawback is that it is unsuited to external uses, or applications where
it is subjected to high-intensity UV radiation.
P4MP is suitable for laboratory ware because it has good chemical
resistance, transparency and high-temperature performance. For medical
ware these same properties are advantageous; in addition, no toxic products

are extracted under normal use. In such applications, additives, such as
antioxidants, must be chosen appropriately.
References
1. Birley, A.W. et al., Plastics and Rubber Processing and Applications 8,337 (1986).
7 Other crystalline thermoplastics
The materials covered in this chapter are the crystalline members of the so-
called 'engineering thermoplastics'. They are rigid and robust, but somewhat
more expensive than the commodity plastics, PE, PP, PS and PVc.
Polyamides and saturated polyesters are used principally in fibres production,
but plastics applications are important; indeed, some materials have been
developed specifically for plastics uses, notably polyamide 11, polyamide 12
and poly(butylene terephthalate). Polyacetals find application as plastics only.
7.1 Polyamides
7.1.1 General-purpose polyamides

The important members of the polyamide family, also known as nylons, and
outline methods of manufacture, are given below.
(i) Polyamide 6.6 (P A 6.6). Obtained from hexamethylene diamine and
adipic acid; stoichiometry in reaction is assured by isolation of 'nylon
salt'. Melting temperature of P A 6.6 is 265°C.
(ii) Polyamide 6 (P A 6). Manufactured by the ring-opening polymerization of
caprolactam: still contains 6% monomer at equilibrium, which is
removed by extraction. Melting temperature of PA 6 is 225°C.
(iii) Polyamide 6.1 0 (P A 6.1 0). Results from condensation of hexamethylene
diamine with sebacic acid: melting temperature 222°C.
(iv) Polyamide 11 (P A 11). Self-condensation of w-aminoundecanoic acid
(obtained from castor oil). Note that cyclic structure is not formed:
melting temperature I85 a C.
(v) Polyamide 12 (P A 12). Prepared by the self-condensation of w-amino acid,
which is obtained from butadiene trimer. Melting temperature 175°C.
Other polyamides have been developed, including polyamide 4.6 (Dutch
State Mines) which, as expected, has a melting temperature higher than that of
PA 6.6, and is intended for service at temperatures above the ceiling for P A 6.6.
Polyamide MXD-6 is the product of condensing metaxylylene diamine with
adipic acid. This polymer has proved to be an outstanding gas barrier; for
example, at 100% relative humidity, it has lower oxygen permeation than
ethylene-vinyl alcohol copolymer (30% ethylene). Otherwise, it is similar to
poly(ethylene terephthalate}, with melting temperature 243°e and glass

transition temperature 64°e, and very similar crystallization behaviour.
However, the polymer does absorb moisture at a level comparable with PA
6.6. PA MXD-6 is finding application is stretch-blow moulded bottles,
sandwiched between poly(ethylene terephthalate}. Aromatic polyamides and
polyimides will be covered later in this chapter.
Proteins are based on amino-acid condensates, i.e. they are polyamides, but
they differ from the simple polyamides listed above, consisting of many
'monomers' in a sequence which is unique to a particular protein.
Polyamides of higher solubility can be made by copolymerization, which
restricts crystallization. The common polyamides P A 6.6 and PA 6 are
frequently oflow molecular weight; the resulting low viscosity requires special
precautions during processing. Extrusion is important for PA 11 and PA 12.
Polymers must be scrupulously dry before processing, otherwise hydrolytic
degradation occurs, with consequent deterioration in properties.
(i) Properties. The properties of crystalline polyamide plastics differ from

those of the polyolefins, considered in the previous two chapters, consequent
on the inclusion of the highly polar amide linkage in their structure.
oII HI
....rvC - N " - f
PA 6 and P A 6.6 have high crystalline melting temperatures as noted above,

and all polyamides are water-attractive, the water absorption (and the melting
temperature) decreasing as the methylene: amide ratio increases, ranging from
8-10% for PA 6 and PA 6.6 to 2-3% for PA 11 and PA 12 at saturation. The
absorption of water affects dimensional stability, each 1% of water absorbed
resulting in an increase in linear dimensions of 0.3% although this may be
partially compensated by post-moulding shrinkage (Figure 7.1). The deform-
ation behaviour is considerably affected by moisture, the effective 'modulus'
~ 1·0
Q)
'Jl
6
~ 0·75
U
c
-5 0·5
OJ
c
Q)
- 0·25
moisture content (%)

Figure 7.1 Polyamide 6 and 6.6: change in dimensions with water content
OTHER CRYSTALLINE THERMOPLASTICS 105
100
III
c...
wet
~ 10
1
o 2 3
strain (%)
Figure 7.2 Polyamide 6.6: effect of water content on isochronous stress vs. strain properties
being reduced to 20-25% of its dry value for equilibrium 'wet' material
(Figure 7.2).
Polyamides have good strength and toughness and excellent fatigue
resistance, the toughness being increased markedly by absorbed water; indeed,
PA 6.6 is brittle when thoroughly dry (Figure 7.3). Electrical properties are not
outstanding, even for dry polymer, and deteriorate further on absorbing
moisture. In chemical properties, polyamides are attacked by acids, but are
stable to alkalis; they are resistant to hydrocarbons, esters and glycols, but are
dissolved by strongly hydrogen-bonding solvents, e.g. phenol.
(ii) Applications. PA 6 and P A 6.6 are used mainly in textiles but find many
plastics uses, usually where toughness is a prerequisite: some examples are oil-
filler caps for road vehicles; teeth in plastics zip fasteners; castors for light
furniture; hopper barrels for food mincers; radiator tanks for cars; hose
connector for Electrolux vacuum cleaner; and gears, especially in food
processing equipment.
20
E'160
......
-,
;-120
0,
c::
~
t)
80
ti
~ 40
.~
O~----~~----~~----~~
-80 -40 0 40
temperature ('C)
Figure 7.3 Polyamide 6.6: impact strength of wet and dry samples
Figure 7.4 Polyamide 6.6: heat-stabilized grade in car radiator header tank
In spite of indifferent electrical properties, PA 6.6 is used by British Rail to

insulate rails from concrete sleepers, as part of the track circuitry for signalling.
It finds wide application in switch components in telephone exchanges, and in
connector harnesses in car wiring. A radiator header tank (Figure 7.4) uses P A
6.6, chosen in respect of its high heat distortion temperature, since the
component frequently experiences temperatures above lOOoe and pressures of
90kNm- 2 .
In spite of a price significantly higher than that of the 'commodity'
polyamides, PA 11 and PA 12 offer a combination of properties which allow
their economic use in a variety of applications. PA 11, which is the longer
established of the two, is more flexible than PA 6.6, is tougher, and is less
affected by moisture. Applications include petrol pipes for cars, hydraulic pipe,
brake fluid reservoirs and film for packaging cooked meat.
7.1.2 Modified polyamides
(i) Fibre-reinforced polyamide. While the cheapest of the polyamides, PA 6

and PA 6.6, offer attractive properties at a competitive price, they have
shortcomings which have been the targets of considerable applied research,
the results of which can be seen in a number of modified grades. The principal
deficiencies are associated with water absorption, and include dimensional
instability, low rigidity at environmental humidity, and a tendency to
brittleness at low humidity. The first two of these were improved by the
introduction of short (2 mm) glass fibres, grades containing 15-40% filler
giving improved solid-state properties, but retaining the capability of being
processed as thermoplastics. The processing of such glass-filled grades is
generally similar to that of the unfilled polymers, but mould design must be
considered very carefully to accommodate anisotropy resulting from flow
orientation of the glass fibres. Mould shrinkage is much reduced, but
anisotropy in shrinkage is usually introduced.
The properties of the glass-filled grades depend on the glass fibre content;
the comments below, and many of the applications cited are for P A 6.6
containing 33% of glass fibres. The specific gravity is 1.39, compared with 1.14
for the unfilled grade and the saturation water content is reduced from 8.5% to
5.8%. The rigidity is increased by a factor of three, even at strains of 2- 3%, and
the strength is enhanced by a similar factor.
Applications are frequently characterized by concurrent requirements of
high rigidity to locate moving parts precisely, and of easy moulding to
complex shapes. Electrical insulation and toughness are added advantages.
Examples of successful applications include: chain-saw housings; body of the
Kango™ electric hammer; cooling fans for commercial vehicles (where
peripheral speeds up to 100 m s - 1 can be tolerated); and a casing for a portable
electric drill, which is discussed in greater detail below. Perhaps less exacting
applications include handles for garden secateurs, electric cooker control
knobs, and a concert clarinet.
The anisotropy resulting from the incorporation of glass fibres in PA 6.6
may be less acceptable to the designer than the somewhat smaller improve-
ment in mechanical properties obtained by addition of up to 40% particulate
mineral filler. The particulate filler gives considerably lower strength and
rigidity compared to glass-fibre-reinforced polyamide, but mould shrinkage
and the effect of moisture on dimensional stability are comparable, and the
processing difficulties associated with the glass fibre filled grade are consider-
ably reduced. However, as often found for particle-filled compounds, the
brittleness is increased significantly.
Early designs of hand-drills involved manufacture of the casing from several
parts. The body was cast, but problems with restricted flow in the casting
operation limited the complexity of the component. The advantage offered by
glass-fibre-filled polyamide was that it could be moulded into a very complex
shape in a single operation, without the need for further machining.
Furthermore, plastics provided a safer product and a reduction in weight. The
main requirements in this product were high strength and rigidity, with good
creep resistance, especially at elevated temperatures, good toughness, close
moulding tolerances, with good dimensional stability, and electrical insul-
ation. An example is shown in Figure 7.5.
Unfilled polymers could be discounted immediately as having insufficient
strength and rigidity and limited creep resistance at high temperature.
Generally, non-fibrous fillers increase rigidity but not strength, so only fibre-
reinforced polymers are suitable. Of eligible materials, ABS, PS-modified PPO
and PP have low strength and heat deflection temperatures, although they
possess good impact properties; filled acetal has properties inferior to
polyamide, polyethersulphone and thermoplastic polyester, and is not
considered further. Polycarbonate is tough but has too Iowa heat deflection
Figure 7.5 Electric drill housing in glass fibre-reinforced polyamide 6.6 (Black and Decker)
temperature for this application. Glass-reinforced polyamide was chosen as

the most suitable material, since it is less costly than polyethersulphone and
gives a better surface finish than glass-reinforced thermoplastic polyester.
Cross-linked plastics generally have unsuitable impact characteristics and
insufficient melt flow to produce this complex component. The high heat-
deflection temperature is necessary because the brush assembly for the electric
motor is connected directly to the plastic drill housing and may be subjected to
a temperature above 200°C. Polyamide has the problem that it is hygroscopic,
but with the addition of glass, the maximum amount of water absorbed is
5.8%, with a corresponding dimensional change not greater than 1.5%. In a
normal room environment at 20°C and 65% relative humidity, the equilibrium
moisture content will be 2% for P A 6.6 with 33% glass fibres. In applications
where closer tolerances are required, glass-reinforced thermoplastic polyester
or polyethersulphone would have to be considered.
(ii) Elastomer-modified polyamides. The tendency of PA 6.6 to brittleness at

low humidity has been a hindrance to its use in some engineering applications.
Grades are now available in which this has been overcome by the addition of
rubber, (frequently ethylene-propylene copolymer elastomer) inevitably with
some decrease in rigidity and strength. The rubber-modified product already
has an impressive list of successful applications, including a vacuum-cleaner
impeller, motor-cycle drive sprocket, handle for rotary hammer and gear for
the starter mechanism of a lawn mower. The same toughening technique
appears to be possible with mineral-filled PA 6.6, the considerable improve-
\
U-- 20 J
, b
20J
~ 0 0 ~
Figure 7.6 (a) Sealer bed pocket in polyamide 6.6 ST (super tough) moulded by Molins Ltd.,
London (b) Application of impact force
ment in impact behaviour allowing use of the compound in automotive parts.

Toughening is again accompanied by some loss in rigidity and strength.
The sealer bed pocket (Figure 7.6.a) is an important component in a
cigarette-packaging machine manufactured by Molins Ltd., London. It
collects into bundles cigarettes which have already been rolled, wraps them in
foil, and forms a cardboard pack around the bundle, operating at a speed of
200 packs per minute. The sealer bed pocket is used to locate the cardboard
while the card is wrapped around the bundle of cigarettes. Several parts of
these machines are made from a special grade of aluminium, which can be
machined easily; however, many of these are not subjected to high stress. The
sealer bed pocket was an application for which plastics seemed to offer an
improvement, since machining the part from aluminium was time-consuming
and produced large quantities of expensive scrap.
When the packaging unit is in use, a pack of cigarettes occasionally becomes
Table 7.1 Impact properties of polyamide materials
Pocket material Impact energy at failure (J)
PA 11 2.6
PA 11 (glass sphere-filled) 1.7
ABS 8.0
Impact modified PA 6.6 21.3 (unbroken)
lodged between the pocket and the card-folding mechanism, causing the
aluminium pocket to break. The impact load was estimated to be 20 J,
occurring at the extremity of the two protruding ears of the pocket
(Figure7.6b). The pocket material requires good wear properties, as the
cardboard slides over the surface at very high speed; further, there is the
possibility of loose tobacco and other cigarette additives becoming sandwi-
ched between the card and the pocket, causing abrasion. Finally, the pocket
must fit well between the guides of the machine to prevent twisting. It was
considered that the most important criterion in materials choice for this
application is the ability to withstand the impact loading. Impact tests on four
materials, simulating the stressing mode, gave the results in Table 7.1,
resulting in the selection of a high impact polyamide 6.6.
Although the impact-modified PA 6.6 gave the best impact performance,
this is slightly offset by the greater distortion in mouldings and the decrease in
strength and rigidity, consequent on toughening (Table 7.2). The component
has been designed with constant section thickness of 3 mm, to reduce
distortion and improve moulded dimensional tolerances. The material is fed
through a sprue, which is recessed away from the main sliding surface, to
enable the sprue to be drilled out easily without interfering with the main
sliding surface.
Monomeric and oligomeric forms of caprolactam modified with a compat-
ible elastomer (such as butadiene) and usually glass-fibre-reinforced, can be
conveniently processed using reaction injection moulding equipment to
produce block copolymers of PA 6, (e.g. Dutch State Mines' Nyrim TM).
Applications include panels for the underside of snowmobiles.
Table 7.2 Properties of dry polyamides
PA 6 PA 6.6 PA II Impact-modified
Property PA 6.6
Tensile strength (MPa) 86 86 58 52

Elongation (%) 20 to 30 40 to 80 300 to 350
Flexural modulus (GPa) 2.75 2.85 1.00 1.76
Notched Izod impact (Jjm) 53 70 210 800
Mould shrinkage (%) 0.6 to 1.8 1.3 to 2.3 - 1.5
Saturation water absorption (%) 9.0 8.5 1.8 6.7
7.1.3 Aromatic polyamides and polyimides
Wholly aromatic polyamides derived from aromatic diamines, such as
phenylene diamine, and aromatic dicarboxylic acids, such as one of the
phthalic acids, are extremely high softening polymers, which are not
necessarily crystalline: they find application as speciality fibres. N omex TM,
derived from m-phenylene diamine and isophthalic acid, is used for re-entry
parachutes for space vehicles and in textiles for firefighters' apparel. Kevlar™,
another condensate of aromatic diamine and dicarboxylic acid, is one of the
stiffest and strongest organic fibres. Since this polyamide contains para-linked
rings exclusively, it is symmetrical and consequently crystalline. Its processing
presents special difficulties, which have been overcome in the case of the fibre
by spinning it in the liquid crystal state, the diluent (or 'solvent') being
sulphuric acid. It is difficult to visualize how this technology could be extended
to plastics use, although Aramid™ resins are available as stock shapes.
Polyimides, again based on aromatic precursors, are noted for their high-
temperature performance, and find some use as high-temperature electrical
insulants. Polyimides are, in one sense, similar to cross-linked plastics in that
they are processed as prepolymers; the final stage of the reaction yields a
product which is still strictly a linear polymer but which degrades before
softening at temperatures over 500°C. This structure allows continuous use in
the absence of air at temperatures up to 315°C with transient surges up to
480°C. However, unlike most cross-linked plastics, this polymer is claimed to
be tough; it is available in semi-fabricated forms from which end-users can
machine their own parts.
7.2 Thermoplastic polyesters
7.2.1 Homo-polyesters
The two most common thermoplastic polyesters are poly(ethylene tereph-
thai ate) (PETP), melting point 265°C: and poly(butylene terephthalate)
(PBTP), melting point 230°C. These two polymers are accessible because of
the widespread use of PETP in fibres and films: they are produced from
ethylene glycol or butylene glycol respectively, condensed with terephthalic
acid or dimethyl terephthalate. The attributes of these polyesters are
properties comparable with PA 6 and PA 6.6, but with considerably lower
water absorption, with beneficial effects on the dimensional stability of
mouldings, and in the retention of mechanical properties in short-term contact
with moisture. PETP presents processing problems in that crystalline
products are possible only at mould temperatures of 140°C, due to quenching
at lower mould temperatures, although a variant overcoming this deficiency is
now claimed. PBTP, also known as polytetramethylene terephthalate
(PTMT), is not so restricted, and crystalline products are obtained directly at
2 20MPa
_.. 20MPa
___________ - - - - Qlass-reinforced
O~ __~~__~~__~~__~~_
1 10 10 2 10 3 10 4
time (hr)
Figure 7.7 Poly(butylene terephthalate): tensile creep at 20 C

D
conventional mould temperatures. A disadvantage of thermoplastic

polyesters is their indifferent hydrolysis resistance: prolonged contact with
water at 95°e, or even at 5o o e, has a significant detrimental effect on
properties. These polymers are characterized by their dimensional stability,
being largely unaffected by changes in the ambient humidity, and by high
rigidity, which is retained to high temperatures. This is particularly true of the
glass-fibre-reinforced grades: illustrative data are given in Figures 7.7 and 7.8.
Although PETP is not widely used as a plastics material, two applications,
one long established and one a more recent development, are important. These
are biaxially oriented film and biaxially oriented bottles, which are suitable for
carbonated drinks. In the manufacture of both products, the following stages
apply:
(i) Melt and homogenize
(ii) Primary shaping (film extrusion or moulding a stubby paris on)
(iii) Quench to substantially amorphous state
(iv) Reheat and orient biaxially, sequentially or simultaneously
(v) Maintaining orientation, heat to crystallize; sets orientation.
100
0·1
-~4nO--~0~--~40~--8~0~~1~2~0--~1~6~0-
temperature ("e)
Figure 7.8 PBTP: tensile modulus vs. temperature
The purpose of the orientation is to improve the barrier properties, while
allowing thinner bottles to be made; rigidity, strength and toughness are also
enhanced.
Poly(butylene terephthalate) (PBTP), a much more recent introduction
than PETP, has already found a number of outlets, including the bodies and
stems of push-button switches on Jaguar cars, valve components for automatic
cattle waterers, and motor mountings in refrigerators for beer chillers. By far
the most important grades are the glass-reinforced plastics, which probably
account for 95% of the PBTP used in mouldings. Examples include terminal
boxes for electricity supply, sextant components, centrifugal pump compo-
nents, parts for a sandwich grill, base and stand for coffee-making machines
and motor end plates in the Vent-Axia 150 domestic extractor fan. Two of
these are considered in greater detail to illustrate the versatility of glass fibre-
filled thermoplastic polyesters; the Vent-Axia fan and the Rima-contact grill. It
appears that grades of PETP, specially formulated for more rapid crystalliz-
ation, offer enhanced stiffness and strength, compared with PBTP, suggesting
use in a number of applications which are currently held by PBTP.
In 1977, the Vent-Axia 150 was developed for the domestic market: special
attention was given in the design to enable manufacture by the cost-effective
injection moulding of most parts. At the design stage, the parts were separated
into two categories: the aesthetic envelope parts, which are subject to minimal
stresses (Figure 7.9), and the mechanical parts, requiring mechanical rigidity
and strength (Figure 7.10). The most important mechanical part is the centre
moulding, because it supports the weight of the electric motor and shutter, as
well as providing accurate location for the rotor and stator of the motor.
Thermosets were discounted for this component, since they are difficult to
Figure 7.9 Vent-Axia fan: aesthetic envelope parts moulded by Derwent Plastics Ltd
Figure 7.10 Vent-Axia fan: mechanical parts moulded by Derwent Plastics Ltd. Centre moulding
is arrowed
mould with intricate detail: thermoplastics materials most suited are fibre-
reinforced versions of polyamide, polycarbonate, thermoplastic polyester,
polyethersulphone, polypropylene, modified polyphenylene oxide and ABS.
Comparison of the mechanical properties of these materials reveals that
polyamide and thermoplastic polyester provide the best balance of properties,
including cost. The centre moulding is always under stress, so creep is another
important factor (Figure 7.11). Other factors affecting choice were dimen-
sional stability and post-moulding dimensional consistency. Glass fibre-
'"
0...
(.!)
6
PS:::;~~====54
'"
~
~'"""::--- 2
~
"0 4
0
E 3
2
10
time (hr)
Figure 7.11 Tensile creep moduli of glass-reinforced
plastics
1. 30% glass-reinforced polypropylene 32°C: 0" = 11.3 MPa
2. 30% glass-reinforced polycarbonate 23°C: 0" = 13.8 MPa
3. 30% glass-reinforced polyamide 6.6 20°C: 0" = 20 MPa
4. 30% glass-reinforced acetal 20°C: 0" = 10 MPa
5. 30% glass-reinforced polyester (PBTP) 20°C: 0" = 20 MPa
reinforced thermoplastic polyester was chosen because it has excellent
mechanical and electrical properties and good fire retardancy.
On the rear side of the centre moulding, a gear needs to be accurately
located, and must rotate easily in the recess provided. This gear meshes with
gear teeth on the seven shutters, each of which is located on one of the seven
studs protruding from the side of the moulding. Thus the tolerances and
clearances between these parts must be controlled accurately to allow the
shutter mechanism to operate satisfactorily. The limits and fits are specified at
the design stage but it is important to appreciate the effects of shrinkage and
after-moulding tolerances. Further, the front side of the moulding has critical
dimensions because it locates both the rotor and stator of the electric motor,
and efficient operation depends on a small and consistent gap between these
components. For glass-reinforced polyester, shrinkage depends on the wall
thickness of 2.5 mm; the shrinkage in the flow direction is 0.25-0.35%, and in
the transverse direction 0.5-0.7%. Tolerances of ± 0.2% are possible provid-
ing the moulding conditions are accurately controlled, and with extreme care,
consistency may be improved to ± 0.1 %, particularly for parts less than 25 mm
in their largest dimension.
A different selection of properties is required in a number of components for
a contact grill manufactured by Rima Ltd, giving considerable savings in cost
and weight, compared with traditional materials (Figure 7.12). Glass-filled
PBTP mouldings provide handles, legs and end-plate unit, hinge bearings,
front handles, temperature control escutcheon and the temperature selector
lever and knob for this electric grill. Material selection required high
temperature resistance and retention of high rigidity to high temperatures;
good impact strength, low thermal conductivity and good chemical resistance
Figure 7.12 Glass fibre-reinforced PBTP components in contact grill (Rima Ltd)
to fats, oils and other domestic chemicals. Intricate design of the mouldings is
possible with the easy-flow plastics materials, and hot runner systems reduce
wastage. The largest moulding comprises a carrying handle, leg supports and
an end-plate in a single unit, replacing four separate metal components in the
original design.
Other thermoplastic polyesters have been reported, including copolyesters
based on 1,4-cyclohexylenedimethylene glycol and terephthalic acid; and
polymers and copolymers of p-hydroxybenzoic acid. Little is known about
established applications. Hot melt adhesives, based on polyesters made from
adipic or phthalic acids with mono- or di-ethylene glycols or 1, 4-butane diol,
find use in shoe manufacture.
7.2.2 Blends of polyesters

Blends ofPBTP and polycarbonate (PC), marketed by General Electric (USA)
under the name Xenoy TM, overcome some of the deficiencies of PC, in
particular, improving the processing behaviour, hydrolysis resistance and
low-temperature impact performance. The amorphous regions of the PBTP
appear to be miscible with the wholly amorphous PC, with the glass transition
of the 50:50 blend at 100°C being intermediate between that of PC (l50°C),
and that of PBTP (35- 40°C). The PBTP crystallizes to a small extent. The
impact behaviour is improved by the inclusion of a small quantity of acrylic
rubber. A demanding application for the 50: 50 blend, with added rubber, is the
Figure 7.13 Front end of Ford "Sierra" in Xenoy CL 1O1™

front and the rear end (fenders) of the European Ford Sierra, illustrated
in Figure 7.13.
The blend, when properly processed, offers toughness down to - 70°C, is
tolerant of recycling, (provided scrupulous care is taken over drying), and is
reasonably resistant to hydrolysis, as shown by immersion in deionized water
at 40°C for 30 weeks.
Finally, blends at different blend ratios are available, e.g. 80:20 PBTP:PC,
which is recommended for improved high-temperature performance (see also
Chapter 11).
7.3 Polyacetals
There are two variants; the homopolymer, which is end-capped with
acetate groups and melts at 175°C, and the copolymer, containing
-CHz-CHz-O-, melting at 163°C.
The homopolymer is polymerized from formaldehyde, and the copolymer is
obtained by copolymerization of, for example, trioxane (a trimer of formal-
dehyde) with ethylene oxide, or dioxane. The homopolymer is stabilized by end-
capping by esterification (treatment with acetic anhydride), or etherification
(dimethyl sulphate). The copolymer is degraded by treatment with aqueous
ammonia to the stable -CHz-CHz-OH end group, which is resistant to
further unzipping. A consequence of these stabilization methods is that the
homopolymer continues to degrade if the chain is broken, or an end-cap
removed, whilst the copolymer degrades only to the next comonomer residue;
also the copolymer is considerably more stable to hydrolysis. On the other
hand, copolymerization restricts crystallization, giving the copolymer lower
rigidity and strength than the homopolymer, and the lower melting tempera-
ture recorded above.
In processing, the most important consideration is that overheating leads to
the prolific liberation of formaldehyde, which is unpleasant and can be
extremely dangerous. Although polyacetals are less hygroscopic than
polyamides, the materials must be dry for processing. Crystallization from the
melt is extremely rapid, with negligible supercooling. Low melt strength leads
to problems in blow-moulding; indeed, polyacetals are mainly used for
injection-moulding and injection blow-moulding. Polyacetals (POM from
polyoxymethylene), have high stiffness and strength, are reasonably tough and
have good dynamic fatigue resistance (Figures 7.14, 7.15). The homopolymer
is some 10-15% more rigid and stronger than the copolymer and is
comparable in impact properties.
The almost simultaneous development of the homopolymer and copolymer
has resulted in competition for the available markets, with more competition
with the advent ofthe thermoplastic polyesters. Generally, the greater strength
and rigidity of the homopolymer promote its preferential use in cams and
gears (illustrated by the case study below); window-winding handles for cars,
... "
. "
,,~O"= 20MPa
.... ...
_ _ _ _ homopolymer
- - - -copolymer
10 10 2 10 3
time (hr)
Figure 7.14 Tensile creep of acetal homopolymer and copolymer
60
~
1;)
Cl
.g 30
III
E
~ 20
iii
10 3 104 10 6
cycles to failure
Figure 7.15 Fatigue resistance of acetal homopolymer
and exterior door-handles for cars and trucks. The copolymer, on the other
hand, is often preferred where chemical resistance and especially hydrolysis
resistance is important: examples include wash basins, taps and other
plumbing items; electric kettles; and the mincer attachment for an electric food
mixer.
The screen-wiper assembly comprises three units: electric motor, gearbox
and oscillating wiper mechanism. We are concerned here with one element of
the gearbox, the wormwheel (Figure 7.16). The system operates initially from
the fast rotation of the electric motor, which is reduced by a worm gear on the
motor shaft driving a plastic wormwheel gear. The main mechanical
requirements for the gearwheel were:
Continuous torque 8J
Maximum excursion temperature 140°C
Maximum continuous running temperature 93°C
Gear ratio (approximately) 50;1
Loading period, continuous 500h
Figure 7.16 Windscreen wiper worm gearwheel in acetal homopolymer moulded by Lucas
Electrical Ltd. Left, an early design; right, modified tooth design for higher torque
The gearwheels were designed to fulfil the 50: 1 ratio, and to be as compact
as possible. The stresses at the base of the gear teeth can be estimated using
beam bending theory: for the teeth in Figure 7.16,
Width of tooth (w) =6.35mm
Addendum and dedendum (/) = 1.98mm
Thickness of tooth at base (d) =2.61mm
Stall torque
Force on each gear tooth (W)
2 x radius of gear wheel
= 148.2 N.
The stress at the base of the gear teeth can be calculated from:
(J M
Y I
where
M = bending moment =WI
I = second moment of area =bd 3
12
Y = maximum distance to top or bottom of beam
= d/2 (for rectangular beams only) whence (J 6WI
= bd 2
= 40 MPa.
The gearwheel must withstand this load after 500 h of continuous operation;
the materials which will survive this loading, excluding glass-filled materials
which will wear badly, are PC, PA, POM, thermoplastic polyesters, and
polysulphones. Cross-linked plastics are too brittle to be considered for gears;
polycarbonate and polysulphone have poor fatigue resistance; polyesters are
suitable, but, being more expensive than polyamides or polyacetals, they are
used less frequently.
Polyamide has superior mechanical properties compared with acetal, but
has the serious limitation that it is hygroscopic. When processing polyamide
the water content must be extremely low; thus, after moulding it contains very
little water and is rigid and brittle. However, PA 6.6 will reach equilibrium
with its environment; in normal conditions of 23°C and 60% relative humidity,
the water content will be about 3%. The ingress of water reduces the rigidity
and strength, improves the impact performance but most important, the
dimensional changes are such that it is unsuitable for gears or for any
component requiring close tolerances when operating in various humidity
environments. Acetal is much more stable dimensionally and possesses
excellent wear and fatigue resistance; thus it is often specified for gears.
Thermoplastic polyesters are used when the application demands better
performance which can justify the increased cost.
Experience in the design of wormwheels was invaluable during this
worm wheel
(a)
worm gear
(b) worm gear
Figure 7.17 Acetal wormwheel; (aj an early design; (b) modified tooth design for higher torque
Table 7.3 Properties of materials for plastic kettle body
Heat deflection
temperature Cc) Maximum water Relative
Material @0.46MPa @ 1.81 MPa absorption (%) cost
Acetal copolymer 158 110 1.6 1.0

Polyamide 6.6 190 75 8.5 1.5
Polycarbonate 145 135 0.6 1.5
Polyethersulphone 203 2.1 5.5
PS-modified PPO 148 103 0.3 1.5
Thermoplastic polyester 179 59 0.7 1.5
Figure 7.18 Kettle body, injection-moulded in acetal copolymer

development, but can be stultifying when changing from metal to plastic. The
first system was a near-identical plastic replacement for metal; a better design
could have been produced if the load-carrying capacity of the parts had been
balanced. Instead, a gearbox was produced which contained a plastic
component, stressed to its limit, and a steel worm, which was lightly stressed.
In later designs requiring more torque throughput, the gearbox was redesig-
ned: the steel worm was reduced to its minimum size, allowing larger and
thicker wormwheel teeth (Figure 7.17). This allowed the gearbox to transmit
50% more torque.
Amongst a miscellany of applications of polyacetals may be cited tenor
recorders: zip fasteners, (replacing metal or polyamide); roller chain and other
conveyor components; counter wheels on petrol pumps; and business
machines. Polyacetals have excellent fatigue resistance, illustrated by their use
in automobile direction-indicating switches.
Metal-bodied kettles are the result of many manufacturing.operations, and
the advantage of a plastic is that it can be moulded in one piece to provide
features to which to attach the electrical element and socket, and provide a
colourful finish, at a cost considerably less than that of the metal part.
Obviously the main requirement is to withstand boiling water; on average a
kettle is boiled for three-minute periods ten times every day. Furthermore, it
should be resistant to attack by fats, oils and other kitchen chemicals, have
good dimensional stability, and resistance to thermal cycling and to stress
cracking.
The most suitable materials on temperature considerations are listed in
Table 7.3. Cross-linked plastics would be suitable thermally and chemically,
but their flow limitations and brittleness prohibit their use. Of the three
materials suitable for use in boiling water, polyethersulphone is very
expensive, and PPO is attacked by some chemicals found in kitchens. Acetal is,
therefore, the most suitable (Figure 7.18); and although the heat stability ofthe
material is suspect for continuous operation at 100°C, (Figure 7.19), it is
100 polyethersulphone (100°C)
c;;-
o. 80 modified PPO (100°C)
:2
.J::
C, 60
c:
~
1;) 40 POlYamide 6.6
.S!
·iii
c:
~ 20
acetal (100°C)
0 4 8 12
time (months)
Figure 7.19 Effect of storage in water at high temperature on tensile strength of various plastics
relatively unaffected by short excursions to this temperature. Acetal homo-
polymer is not suitable for contact with water above 60°C; however, the
copolymer is satisfactory and has been used since 1969 for hot-water plumbing
applications. An advantage over metal is less scaling, and grades are available
which satisfy the toxicity requirements of the United States Food and Drugs
Administration. Another candidate material for this application is impact-
modified polypropylene.
Glass fibre-filled grades are available with enhanced rigidity and strength,
but they do not appear to be used widely.
8 Vinyl chloride plastics
Poly(vinyl chloride), PVC, is one of the most versatile of polymers, and the
following forms have important applications: rigid (unplasticized) grades,
plasticized compounds, copolymers and blends. This is perhaps surprising
since it is one of the least stable polymers, for which reason much of the early
development was concerned with copolymers and with plasticized
compositions.
The monomer is now almost exclusively obtained from ethylene, which has
displaced the older acetylene-based process. There is some evidence that vinyl
chloride is carcinogenic and there are legal requirements limiting exposure to
the monomer.
Polymerization is by free-radical-initiated reaction, in either suspension
or emulsion processes in water at about 50°e. In the suspension process,
polyvinyl alcohol, incompletely hydrolysed PV AC, or gelatine, are used as a
colloid stabilizer with peroxide initiators. The emulsion process employs
emulsifiers, such as sodium lauryl sulphate and water-soluble persulphate
initiators. Mass polymerization gives PVC powders with characteristics
different from those of suspension polymer.
Whilst the chain linkage is substantially head-to-tail, there is still con-
troversy over the amount oflong-chain branching involved. Commercial PVC
has a small amount of crystallinity (about 5-15% depending on the thermal
treatment), being syndiotactic in nature. It has an important influence on
properties, not always beneficial, and must be considered explicitly in
processing and implicitly in data for design. The crystallizability can be
increased by polymerizing at low temperature, but such polymers are not
commercially important. Molecular weight is an important variable, being
recorded as the K value, which is derived from solution viscosity measure-
ments. K values from 45 to 90 (cyclohexanone) cover number-average
molecular weights from 25000 to 85000.
8.1 Unplasticized poly(vinyl chloride) (UPVC)

Because of its limited thermal stability together with the low amount of
crystallinity, the melt viscosity of PVC is very high at normal processing
temperatures. Therefore, thermal stabilizers and lubricants are essential
ingredients for processing. Instability is usually assessed by colour change,
resulting from hydrogen chloride evolution which leaves an unsaturated
VINYL CHLORIDE PLASTICS 125
chain, although degradation is a complex reaction in which oxygen is
involved.
Some stabilizers are effective in improving weathering behaviour. Lead
compounds are good heat stabilizers; basic lead carbonate or tribasic lead
sulphate are favoured stabilizers but are toxic. The stearate, palmitate and
octoate salts of Cd, Ba, Ca, Zn are increasingly used, but toxicity limits the
range of applications for Cd. Organo-tin compounds are also effective
stabilizers, especially for transparent products, but may also be somewhat
toxic.
Successful processing of unplasticized or rigid PVC (UPVC) requires
lubricants, such as lead or calcium stearates, stearic acid or hydrocarbon
waxes. UPVC is frequently extruded, and so lubricants melting at lOO-120°C
are most effective for extrusion at 165°C. UPVC is also widely used in sheet
form, obtained by compression moulding multiple plies of calendered foil.
Sheet is manipulated by heating and shaping (thermoforming); it is
frequently welded or cemented with solvent-based adhesives. UPVC com-
pound can be injection-moulded using a screw pre-plasticizer.
PVC is a rigid material and is tough under ambient conditions if stress
concentrations are absent (see Figures 8.1, 8.2). The softening point is 85°C,
but PVC is not reliably load-bearing above 60°C. It is resistant to water and
hydrocarbons, but is soluble in polar solvents, although high temperature may
be required to effect solution. Typical applications include pipe, rainwater
goods (by extrusion) with fittings (by injection-moulding); sheet used in
hygienic cladding; extruded sheet sections which lock together, e.g. to form a
compost bin for horticulture; sheet welded into battery overspill boxes for
lifeboats; clear bottles of 125, 250 and 500 ml capacity; curtain rails; and
domestic window frames.
Until the 1950s, lead provided the best corrosion resistance in drainage
pipes, with cast iron being the cheaper choice. The shortage and high price of
lead then forced local authorities to seek alternative materials. Polyethylene
PVC PMMA
/
E 150 unnotched:
:; I
I
S 100
~
,
i
~ I PVC
50 _ ... / I ~.T notch

.~ ~"'::~PMMA
-80 -40 0 40
temperature (·C)
Figure 8.1 Impact behaviour of PVC

1·5 60·e
~ 1·0
~ (1= 10MPa
c:
.~
en
20·e
0·01 0·1 10 10 3
time (hr)
Figure 8.2 Comparison of creep of PVC at 20 0

e and 60 e
0
and upve were found to be not only suitable, but also offered several
advantages: corrosion resistance, longitudinal flexibility, ease of installation,
smooth internal bore, and economy. upve was preferred over polyethylene
for drainage systems because of its rigidity and ease of jointing by solvent
welding. BS 4514: 1983 provides that pipes for domestic drainage have to
withstand short exposures to water at 91°e and a rest period of 60 seconds,
repeated for 2500 cycles. In rainwater goods applications, upve is chosen
because it combines rigidity, low cost, good UV stability, good chemical
resistance, and ease of assembly and joining. The above-ground system is
usually coloured grey, the below-ground system brown.
The below-ground system has to withstand the temperatures specified in BS
4514, but also the loads imposed by soil cover. The recommendations for such
a pipe are a minimum wall thickness of 3.4 mm for a nominal inside diameter of
100mm. BS 4660: 1973 provides for all underground drainage systems to resist
the crushing load of backfill. The grade ofUPVe chosen for these applications
must have a Vicat softening point not lower than 81°e, with 79°e at a 49 N
load for fittings when tested to BS 2782: Part 1: 1976 (1983), method 120B.
12
r0-
c..
~ 8
en
en
~
1;)
c: 4
Cl
·iii
Q)
"C
0
0 15 30 45 60
temperature ee)
Figure 8.3 PVC: effect of temperature on design stress
Many companies have obtained Agrement Certificates for their own designs
of underground drainage systems. UPVC has faced limited competition from
other polymeric materials in these applications, but with the exception of
drainage inspection chambers, UPVC has not been displaced. Drainage
inspection chambers are complex units with several inlet and outlet ports
which are injection-moulded in ABS or newer grades of HDPE, or fabricated
from GRP. For pipes, UPVC has stood the test of time, having the best
combination of properties - rigidity, chemical resistance, solvent welding and
60
ro
a..
~
'"'"~
lii ---
~
a.
:J
20
2
0·01 10 2 10"
time (hr)
Figure 8.4 UPVC: creep rupture at 20°C
Figure 8.5 Selection of UPVC drainage pipes and fittings (Yorkshire Imperial Plastics) Photo-
graph by courtesy of ICI Ltd
cost. The other cheap commodity plastics, polypropylene and polyethylene,

generally are less rigid, difficult to join (although recent developments of on-
site electrothermal welding, or friction-fit jointing have reduced this problem),
and have poorer UV resistance, but have better chemical resistance.
BS 3505: 1968 (1982) recommends a design stress for UPVC of 12.3 MPa at
23°C for cold-water service pipe (Figure 8.3). This standard requires the pipe
to be in service for 50 years, corresponding to 30 MPa rupture stress
(Figure 8.4). This gives a safety factor of about 2.1. However, as pipes in service
will suffer from poor installation, external abrasive materials (e.g. broken
bricks and stones), or simply poor manufacture, external and internal
pressures will cause a pipe to fail at a stress much lower than 30 MPa. In
critical applications it is preferable to design using fracture mechanics; indeed,
a fracture toughness of UPVC is specified in BS 3505: 1986. This results in a
design stress of approximately 6 MPa. Figure 8.5 shows a selection of UPVC
pipes and fittings.
8.2 Plasticized poly(vinyl chloride), (PPVC)

Plasticizers are high-boiling liquids which are solvents for PVC; increasing
addition reduces the Tg value of PVC until the material is rubbery, usually at
levels above 30 phr by weight. Most commonly used plasticizers are C s to C lO
derivatives of phthalic acid, e.g. dioctyl phthalate (DOP) and didecyl phthalate
(DDP): the latter is less water-extractable, hence finding use for baby-pants.
Phosphate plasticizers (e.g. trixylyl phosphate) are more expensive, more toxic
but effectively enhance fire resistance. Aliphatic acid esters with C s to C 10 are
normally used in combination with phthalate plasticizers.
Polymeric plasticizers, such as poly(propylene adipate) and poly(propylene
sebacate), are non-volatile, non-migratory and resistant to hydrocarbon
extraction. However, they are expensive and the compounds are difficult to
manufacture. Extender plasticizers are not compatible with PVC but are
miscible with plasticized PVc. A processor can use them to replace a part of
the more expensive plasticizer content. Examples include chlorinated paraffin
waxes, paraffin liquids or oil extracts.
Compounding of plasticizers, stabilizers and other additives into PVC is as
critical as the subsequent shaping. Suspension-grade PVC is normally dry-
blended using high shear mixers to produce powders for melt processing, e.g.
calendering and extrusion. Emulsion-grade PVC compounded with levels of
plasticizer above 20 phr tends to form free-flowing pastes (mixtures of
plasticizer-swollen PVC particles suspended in the remaining liquid
plasticizer - this will also be absorbed by the PVC, the rate depending on PVC
resin, plasticizer, and temperature); these are also known as plastisols. A wide
range of compounding equipment is used, from low-shear ribbon mixers to
high-shear impeller mixers, preferably operating under vacuum to minimize
air entrapment. Pastes lend themselves to spread, dip, screen and spray-
coating, and the simpler shaping techniques such as pour casting and
rotational moulding.
The controlled absorption of the plasticizer by the PVC particles is an
essential part of the process, and this depends on particle size and texture.
Paste viscosity depends on particle size and distribution. Paste storage life
depends on plasticizer type (for instance, butyl benzyl phthalate, BBP, will
produce rapid solvation and viscosity increase, compared with DOP), and the
residual emulsifier left on the PVC particles: both these paste properties are
dependent on its thermal history. Additives, such as inorganic fillers, will also
have a marked effect on paste properties. Increasing the temperature of a paste
increase plasticizer absorption and viscosity. Eventually all free plasticizer will
be absorbed, with the swollen PVC particles in contact with each other and
limited fusion occurring across particle boundaries. In this so-called gelled
state, the plasticized PVC will be dry to the touch and have minimal strength.
Further heating will increase the degree ofJus ion between the particles of PVC,
until optimum mechanical properties result. The particle structure is very
durable and indeed will be retained at process temperatures up to 170°C.
Homogeneity or full fusion will occur above these temperatures as the PVC
increasingly takes on the behaviour of a true thermoplastic melt, with relative
movement within the molecular structure. Full fusion, indicated by maximum
mechanical properties of a tough rubbery product, depends on heat input,
previous thermal history, PVC type, plasticizer type and content, and other
additives.
At lower additions of plasticizer (up to 10 phr), the expected softening
behaviour is reversed and the compound increases in hardness and Tg • This
anti-plasticization has been explained by increased crystallinity facilitated by
plasticizer.
Other additives are used. Fillers serve both technical and economical
purposes: china clay enhances electrical properties, but calcium carbonates
and asbestos are also important. Pigments are used as coloured fillers:
titanium dioxide acts as an intensive whitener and will reinforce the colouring
effect of printing inks applied to the PVC substrate. Chemical blowing agents,
such as azodicarbonamide (AC), break down to form gases during processing
which expand PPVC into a cellular or foamed product. Cd stabilizers will also
catalyze this breakdown, allowing the blowing action to be activated at lower
temperatures. Because of the higher price of emulsion PVC, pastes are often
made from resin blends including micro-suspension grades of PVC (up to
30%), known as extender resins; these also increase storage stability without
sacrificing mechanical properties. It is important to note that increasing levels
of phthalate plasticizers will reduce the fire resistance inherent in UPVC
products.
Products made from PPVC based on suspension-grade polymer include
calendered sheet; domestic electric cable; commercial damp courses; garden
hoses made by the extrusion process; and automotive door seals and draught
excluders made by the simultaneous co-extrusion of several grades of PPVC

containing different levels of plasticizers. Figure 8.6 includes a few of the wide
range of goods made from plasticized PVc.
Table 8.1 indicates the annual consumption of emulsion-grade PVC used in
plastisol processes. The major use of emulsion-grade PVC has been in sheet
Figure 8.6 A selection of goods made from suspension. emulsion and copolymer grades of PVc.
Permission of Wacker Chemicals (UK) Ltd
Table 8.1 Uses of emulsion-grade PVC in the UK, 1985. Permission of Wacker
Chemicals (UK)
Applications Approximate tonnage used
Sheet vinyl cushion flooring 28000

Wall covering* 20000
Metal cladding 10000
Conveyor belting 7000
Dip coating (e.g. gloves) 5000
Car underseal 1500
Total including miscellaneous applications: 80000 to 85000
*For 1986, it has been estimated that high profiled wall coverings based on foamed
PPVC, probably used as much as 10000 tonnes of PVc.
Figure 8.7 Micrograph showing the typical structure of a modern sheet vinyl flooring, made up of:
(A) glass-fibre reinforced PPVC, (B) foamed PPVC, (C) decorative film based on printing inks, (D)
clear PPVC wear layer. By permission of Armstrong World Industries Ltd
vinyl flooring, although structures have changed markedly over the last 20
years. Modern floor-covering is based on a composition of at least four
laminates of diverse PPVC compositions, as illustrated in Figure 8.7.
Typical of many manufacturing methods, Armstrong's Rhinofloor™ sheet
vinyl flooring is made up as follows. An inorganic particulate-filled paste is
made up from phthalate and other plasticizers (approximately 60 phr) in a
blend of PVC resins (e.g. K = 70 emulsion resin and up to 30 phr of extender
suspension resin at K = 55 to 65). This is reversed-roll or knife-over-roll coated
into an open glass-fibre (non-woven) scrim: the paste is gelled at 150°C to give
limited mechanical strength. A foam able plastisol, containing a paste of AC
blowing agent and titanium dioxide as a whitener, again based on a mixture of
emulsion and suspension resins with fillers, is applied and gelled at 140°C
without activating the blowing agent. The structure is rotogravure printed,
applying up to five ink colours normally based on acrylates. Some of the ink
will include an inhibitor to prevent the catalysis of the AC in the fusion process.
The gelled PPVC should have enough strength to resist the pressure of
printing. The structure goes back to the coating line for application of a clear
wear layer. This must be transparent and be both abrasion- and stain-
resistant; it is based on emulsion-grade PVC of relatively high K values, to give
the required mechanical properties, in a plasticizer blend (e.g. DOP, BBP and
secondary ester plasticizers to 60- 70 phr total; the BBP is included to enhance
stain resistance). Again the temperature of the oven is selected for gelation of
the wear layer. Finally, either a solid or foamable back coat is applied to the
back of the structure; the whole product is passed into an oven at 170-195°C,
where fusion and foaming are completed. At the same time chemical
embossing in-register is imparted by inhibiting the blowing action of the AC in
selected parts of the flooring.
8.3 Vinyl chloride copolymers

Copolymers of vinyl chloride with vinyl acetate (V AC) prepared by granular
polymerization are the most important. As crystallinity of the PVC is almost
certainly eliminated by copolymerization, a typical copolymer with 13% VAC
has a lower Tg and much improved flow properties, compared with the
homopolymer.
Unplasticized copolymer is used for gramophone records; the chief
demands for this product is quality of sound reproduction and reasonable
cost. The four cheapest materials (polyethylene, polypropylene, polystyrene
and PVC) could be considered, but polypropylene and polyethylene are both
crystalline and exhibit larger shrinkage than amorphous materials. In
addition, polyethylene tends to smooth out any sharp features (the record
groove), and polypropylene, although it follows the mould surface, has high
shrinkage; therefore neither is a suitable material for sound reproduction.
Polystyrene is too brittle and has poor wear properties. Although the vinyl
chloride homopolymer has some crystallinity, vinyl acetate in the copolymer
inhibits this, giving an amorphous material which has good-quality reproduc-
tion, good wear properties, comparatively low cost and high durability. The
copolymer is relatively cheaper to process than the homopolymer, having
improved melt flow properties and a lower processing temperature.
The copolymer is blended with several additives to improve the perfor-
mance of the record. For example, static charge can accumulate on the record
surface, impairing the sound reproduction: antistatic agents such as quater-
nary ammonium salts have some limited value in solving this problem. Fillers
cannot be tolerated in this application, although pigment is included, and
stabilizers and lubricants are chosen to produce minimum surface noise. A
typical formulation for records is:
phr
Vinyl chloride/vinyl acetate copolymer (VC/VA, 87: 13) 100
Dibasic lead stearate (lubricant/stabilizer) 0.75
Dibasic lead phthalate (stabilizer) 0.75
Lamp black (pigment) 2.0
Records are moulded using pre-heated extruded compound (dough) at 130-

140°C; the cycle time varies from 20-30 seconds. It is possible to mould
records in an injection/compression sequence on an injection machine. The
machine operates in the conventional way, except that the mould is not
completely closed (about 6 mm clearance), the melt is injected into the cavity
space and then the mould is closed. However, the injection/compression
method produces inferior records in respect of reproduction quality.
The main use of the vinyl chloride - vinyl acetate copolymer is in the
production offlooring tiles. Typically, tiles contain 30-40 phr of plasticizer and
300-400 phr offiller (e.g. chalk, asbestos, pigments). The mix is dry-blended in
an internal mixer and calendered.
8.4 Blends of poly(vinyl chloride)

PVC which has been processed competently, and where high stress con-
centrations are absent, has impact properties which are quite acceptable, as
may be judged from the list of applications given above. However, there are
designs for which increased toughness is demanded. PVC will form blends
with a number of polymers, in both single and multiple combinations. The
PVC is permanently plasticized by the other polymer(s) and the resulting
material should ideally have a combination of the parent polymer properties,
or better. Miscibility of any blend is not essential to produce property
enhancement and is dependent on polymer types, their ratio and compound-
ing method.
PVC with chlorinated polyethylene blends has improved impact perfor-
mance, especially in the presence of notches and at lower temperatures than
unmodified grades of PVc. They are used in continental Europe for external
applications (e.g. rainwater goods); unmodified UPVC would be acceptable in
the UK. Such blends are finding increasing use throughout Europe in
extruded sections for window frames.
PVC blended with ABS or impact-modified PMMA has improved
processability and good fire resistance, along with impact properties superior
to those of the parent polymers. ABS/PVC is used as calendered sheet
thermoformed into car crash-pad skins (subsequently back-filled with semi-
rigid PU foam), also in moulded power tool handles, sanitary ware and
electrical housings. Impact PMMA/PVC is used for seat backs for public
transport and industrial panelling.
PPVC is blended with high-molecular-weight elastomeric materials, such as
nitrile rubber (NBR), EV AC and polyurethane (PU), to improve the shock
resistance of flexible compounds. PPVCjNBR blends have good oil resistance
and are used to make industrial boot-soles and in some electrical cable
applications. PVC/EV AC and PVC/PU are used in shoe-sole formulations.
8.S Vinylidene chloride polymers and copolymers

A considerable number of other chlorinated polymers find commercial use as a
means to impart fire retardancy into a product. Poly(vinylidene chloride)
(PVDC) and its copolymers are described here, particularly because of their
gas and vapour barllier properties.
Vinylidene chloride is produced by the dehydrochlorination oftrichloroeth-

ane at 400°C. The monomer is difficult to handle because of its flammability,
toxicity and its readiness to autopolymerize. The monomer is normally
suspension polymerized using peroxide catalysts at 0-20°C: emulsion and
bulk methods are also used. The polymer has a regular molecular structure,
giving rise to high crystallinity, high specific gravity (1.875) and low
permeability to gases and vapours (up to a thousand times better than LDPE).
The high chlorine content in the polymer produces excellent fire resistance but
also leads to rapid degradation at normal process temperatures.
Copolymerization by suspension or emulsion methods, with vinyl chloride
or acrylonitrile for example, reduces the regularity in the chain, increasing
flexibility and permitting processing below the copolymer's degradation
temperature. Copolymers are readily crystallizable, and care is needed in the
setting of process temperatures for extruded (e.g. pipe) and moulded goods.
The polymer and its copolymers are mainly exploited for their barrier
properties, both as film and coating materials. The major use for homopoly-
mer and vinyl chloride copolymer is a surface coating for PETP bottles, to
enhance their oxygen barrier properties, when the bottle is to be filled with a
carbonated alcoholic beverage: alcohol may be oxidized to acetaldehyde,
which taints the flavour of the drink. The outer surface of the bottle is dip-
coated in polymer as a latex, and dried at about 60°C (i.e. below the Tg of
PETP), to form a bonded, coherent film on its surface. The biaxially oriented
film has excellent mechanical and optical properties. The copolymer is also
made into fibres which have excellent mechanical properties, durability and
chemical resistance (they are used in deck-chair fabrics for example).
The acrylonitrile copolymers find limited use in the production of cast film
for coated cellophane, polyethylene and paper.
9 Speciality thermoplastics
A number of thermoplastics produced in small quantities worldwide have

already been described within the appropriate families of materials in earlier
chapters, for example polyamides and polyimides. The present chapter
accommodates the more important members of the thermoplastic groups not
included in other sections. These include fluoroplastics, polysulphones and
sulphide polymers.
9.1 Fluoroplastics
Poly(tetrafluoroethylene) (PTFE) is the oldest member of this family, having
been available since the early 1950s, yet worldwide production is only a
few thousand tonnes per year. Even so, PTFE is the most commonly used
fluoropolymer, widely used in specialist applications by engineers. This is
primarily because of its unusual properties, notably high melting temperature,
extreme chemical inertness and an extremely low coefficient of friction for
either PTFE-metal or PTFE-PTFE contact. On the debit side, PTFE has an
inherently high price and is very difficult to process, which is principally
associated with the extremely high viscosity of the molten polymer. Many
attempts have been made to improve the processing behaviour, mostly by
copolymerization, without sacrificing too many of its desirable characteristics.
A limiting compromise is to substitute other fluorine-containing homopoly-
mers such as poly(vinylidene fluoride), into part of the PTFE molecular
structure; these do not present processing problems, but unfortunately they do
not have the very desirable properties of PTFE.
Poly(vinyl fluoride) is included, although it shows greater similarities to
poly(vinyl chloride) than to the other fluoropolymers. It also should be
mentioned that a wide variety of fluoropolymer elastomers is used under
extreme conditions of temperature and chemical environment.
Fluorine-free polymers find particular use in high-temperature and
corrosion-resistance environments, and some consideration will be given to
them in this chapter.
9.1.1 Poly( tetrajluoroethylene)

There is a large number of companies manufacturing PTFE: this is surprising
when the difficulties and hazards associated with the industrial preparation of
the monomer and its polymerization are taken into account. Suspension and
emulsion polymerization are employed to give materials suited to particular
processing methods. Further, to obtain optimum properties in the final
product, work-up operations for the polymer must be carried out under
rigorously dust-free conditions.
Experimental and theoretical evidence indicates that suspension poly-
merized (granular) PTFE is a linear and unbranched polymer, with a
molecular weight exceeding half a million. PTFE has the comparatively high
specific gravity of 2.28, and the virgin polymer has very high crystallinity, 90-
95%, and a melting point of 340°C. However, after melt processing the
crystallinity is not fully regained, dropping to between 50-70% with a melting
temperature of 328°C. A reversible volume increase of about 30% takes place
between 15°C and the melting point. Above the crystalline melting point, the
'melt' has a very high viscosity, typically a million times greater than for most
thermoplastics: this precludes normal thermoplastic processing methods.
Lower crystallinity, and consequently density, are associated with higher-
molecular-weight polymer. This is a useful relationship, since the normal
solution methods of molecular weight determination are precluded by the
insolubility of PTFE in all solvents except at temperatures above 300°C, which
property is exploited in many applications. PTFE is chemically inert, attack
being limited to materials such as molten sodium. It may be dissolved by
highly fluorinated liquids near its melting point. It has excellent weathering
resistance and is stable in air to at least 250°C for continuous service.
Very low coefficients of friction are obtained for PTFE-PTFE or PTFE
with most metal systems: as a corollary, nothing will stick to PFTE. The low
critical surface tension ofPTFE (18 mNm -2) prevents wetting and subsequent
adhesion by adhesives or surface coatings, unless the PTFE is pretreated (e.g.
by plasma or sodium xanthate etching). Dielectric losses are very small,
particularly for unsintered material, and volume resistivity is very high.
Mechanically PTFE is tough and moderately flexible with a high elongation
to break. Toughness is retained at very high and very low temperatures: PFTE
is one of the few materials which does not embrittle at liquid-helium
temperatures. On the other hand, PTFE creeps under moderate stress, a
design consideration and possible limitation on the engineering use of the
material. Recovery from deformation is poorer than for other thermoplastics.
Many applications of PTFE involve compression (see Figure 9.1), and
therefore compression creep is important: representative creep data are given
in Figure 9.2.
Although PTFE is a linear-chain polymer and a thermoplastic, its extremely
high melt viscosity does not permit the usual thermoplastic processing
technology. Instead the methods of powder metallurgy are adopted: pressure
preforms are sintered at temperatures above the crystalline melting point,
typically 380°C. Complicated shapes are obtained by machining, making
products very expensive. Powder processing is a compromise between powder
SPECIALITY THERMOPLASTICS 137
Figure 9.1 PTFE expansion bellows: weight 7 kg. Made by Henry Crossley (Packings) Ltd.,
Bolton, from Fluon TM. Photograph by courtesy of lei Ltd
flow and good strength; particle shape, size, size distribution, external
topography and internal structure are all important. Some highly toxic cyclic
fluoro-compounds are liberated by heating PTFE to sintering temperatures,
so good ventilation is essential. Extrusion, particularly of thin sections, is
accomplished by lubricating dispersion PTFE powder with petroleum ether,
and subsequently drying and sintering the extrudate {tube for example}.
Unsintered tape is obtained by calendering.
Applications cover nearly all property regions. PTFE is exploited for non-
stick coatings in a variety of applications, including cookware, bread
processing, toffee-making and coating on skis. Bearings, particularly com-
posite systems, frequently involve PTFE. An exacting application is in
suspension bushes used in some rally cars, which have been spectacularly
successful. Chemical inertness in the presence of biological fluids is one basis
for the many medical applications of PTFE: a typical use is in the catheters
used in dialysis equipment employed in the treatment of renal failure. PTFE is
widely used for critical electrical insulation, but polyimides and polyketones
e:.
c:::
.~
en
Q)
>
·iii
en
Q)
0.
E
o()
o~ __~__~____~__~~__~_
0·01 0·1 10 10 2 10 3
time (hr)
Figure 9.2 Compressive creep curves for PTFE: 20 u C, 6.9 MPa
are now preferred for wire coating applications. The unsintered, extended
material is used by plumbers, as tape for sealing threads. Valves, gaskets,
expansion bellows are typical uses for PTFE. An example is an expansion
bellows (Figure 9.1), in a glass-reinforced polyester pipeline carrying wet
chlorine gas. In a large chlorine-producing plant, chlorine is piped to the
cleaning and drying units together with brine mist at low pressures (14 kPa or
2 psi) and at a temperature of 70-80°C. Transporting this corrosive mixture
presents several problems, the greatest of which is to provide corrosion-
resistant pipework of long life. Furthermore, the pipework should allow for
expansion and contraction with changes in temperatures. Polyester resin was
chosen for the pipework but the existing rubber-based expansion bellows had
a short service life, only 12-18 months. PTFE was recommended for this
application and ensures that the bellows have a virtually unlimited life. As its
reliability means no lost production, the bellows are much more cost-effective
than rubber, although much more expensive initially.
Many of the properties of PTFE depend on the characteristics of the
particles (which can be affected by polymerization technique) and on the
processing conditions, including moulding pressure, sintering temperature
and time, and heating and cooling rates. Crystallinity and porosity are
affected, which in turn influence properties such as strength, modulus,
hardness and permeability. Fillers are used in PTFE to give particular
technical effects rather than, as might be expected, to reduce the cost. Creep
behaviour is improved by inclusion of short glass fibres (Figure 9.2); the
excellent frictional characteristics are further enhanced by incorporating
graphite or molybdenum disulphide, or both; metal powders increase thermal
conductivity thus reducing overheating and consequent failure in bearings.
9.1.2 Poly( vinylidene fluoride)

Poly(vinylidene fluoride) (PVDF) is a fluoropolymer which shares some
properties, including high cost, with PTFE. It contains the repeat unit
-CH 2 -CF 2 - ' explaining its chemical inertness, but it will degrade at
high temperatures (380-400°C), liberating HF. It has a crystalline melting
point of 170-171 0c. The various grades of PVDF homopolymer are available
for most thermoplastics processing methods without significant degradation
at 220-240°C. PVDF is incompatible with other polymers (except acrylics)
and the melt may be degraded by impurities. Therefore process equipment
must be scrupulously clean and care must be exercised in the selection of
pigments, although PVDF may be recycled at normal melt temperatures.
The properties of PVDF are influenced by its molecular weight, which also
strongly affects processing and the crystallinity level achieved. Generally, the
properties are not strongly dependent on operating temperature in the range
60-150°C; this leads to applications in chemical plant, transport and aero-
space. In such applications as pipes, pumps and fittings, poly(vinylidene
fluoride) is resistant to halogens, oxidants, strong bases and acids (except at
high temperatures); it is less resistant to polar organic solvents. One of its main
application areas is in chemical process plant, PVDF having good strength
and impact resistance and outstanding resistance to abrasion/erosion. This
exceptional property has led to the satisfactory use of PDVF as a coating on
propellers for high-performance water craft. Representative creep data are
given in Figure 9.3.
The resistance of PVDF to y-radiation is exceptional; the material is little
affected even by a dose of 300 Mrad from a Co 60 source. In the reprocessing of
nuclear waste, reliability of the equipment is of the utmost importance.
Reliability has to be maintained during the handling of corrosive liquids such
as nitric and hydrofluoric acids at 105-11O°C, while exposure to high-energy
radiations is also a major consideration in this application. On all these
counts, PVDF shows satisfactory behaviour, making it a recommended
material for pipework in this exacting application.
Its resistance to ageing and weathering is excellent, and so it finds ready use
in polluted industrial locations: eight years' exposure in such an environment
~ 3
c
.~
2
(J)
13·8MPa
0
0·1 10 10 2 10 3 104
time (hr)
Figure 9.3 Poly(vinylidene fluoride): creep curves at 20 c e

is one example resulted in only marginal change in mechanical properties.

PVDF is also self-extinguishing.
Filled compositions are available, but it must be remembered that fillers can
reduce the stability of the polymer or introduce instability in their own right,
glass beads reduce stability in the presence of hydrogen fluoride, for instance.
Filled compounds show markedly lower shrinkage and higher rigidity;
toughness is generally decreased.
Copolymers of vinylidene fluoride and tetrafluoroethylene are available,
characterized by lower crystallinity and melting point, with greater flexibility,
extensibility and toughness. Otherwise they are generally similar to the
homopolymers.
9.1.3 Other jluoropolymers

Polyvinyl fluoride (PVF) is generally similar to PVC, but is tra9sparent to UV
radiation and therefore has excellent weathering resistance. It is used in
laminates because of this property. Its brittle temperature is very low,
- 165°C.
Polychlorotrifluoroethylene, (PCTFE) is less crystalline and less inert than
PTFE: it can be shaped by normal thermoplastic melt processing methods.
Because of its relative transparency, it finds limited use as observation
windows (in sheet form), or as specialist tube material.
Other fluoropolymers are produced in small quantities and for specific
applications, including copolymers of ethylene with chlorotrifluoroethylene
and TFE.
9.2 Polysulphones
These plastics are characterized by having the sulphone group -SOz-as a
constituent in a polymer structure consisting largely of aromatic groups,
generally linked in the para-position (p-phenylene). Thermal stability in air,
high softening temperature and good mechanical properties are attributes
leading to an increasing interest in a variety of applications, in spite of their
high cost. Polysulphones can be readily processed by conventional thermo-
plastic techniques although their softening temperatures exceed 200°C.
Polysulphones may be formally expected to have regular and linear
structures, but in fact most types contain a 'kink' or 'dog-leg' which inhibits
crystallization. This similarity exists in the polycarbonates, and it is presumed
that the reluctance to crystallize is related to similar structural features.
C H3 0
'V f -0 O-C-O~
~~I~ II
C H3
(i) Polycarbonate
(ii) poly suI phone, e.g. Udel™ Polysulfone (Union Carbide), softening point 190°C
(iii) Polyethersulphone (softening point 220°C)
Therefore, most commercial polysulphones are available as amorphous

materials, which consequently are transparent after melt processing. There is
an exception in the family, which does not possess the 'kinked' feature (iv);
this is a crystalline polymer having a melting point exceeding 500°C, at which
temperature it will be also starting to degrade:
o
~~~
o (iv)
Crystallinity is not a characteristic of the commercially significant polysul-

phones, which consist of the homo polymers (ii) and (iii), together with a range
of copolymers based on (iii) and (iv). The inclusion of increasing amounts ofthe
latter increases the softening point of the polyethersulphone.
Exemplifying the design properties of these materials by reference to data
for polyethersulphone, creep data for unmodified and glass fibre-reinforced
grades are given in Figures 9.4 and 9.5 for 20°C and 150 a C, and for strength as
a function of temperature in Figure 9.6. Impact data indicate that the material
~-c
.~
2 L------------------?O~!5c~
20'C 50 MPa ---
1;;
~
.iii
c
!!l
__------------------,~a
0'1 10 10 2 10 3
time (hr)
Figure 9.4 Creep curves for polyethersulphone at 20°C and ISOaC
~
c
.~
en
~
"iii
c 20% glass fibre
~
0
0"1 10 10 2 10 3
time (hr)
Figure 9.5 Tensile creep of polyethersulphone at 150°C, 20 MPa: effect of glass fibre
reinforcement
100
rf. 80
2:
.I:
60
C,
c
~en 40
~
"iii
c 20
~
o 50 100 150 200

temperature ('C)
Figure 9.6 Tensile strength of polyethersulphone
is tough at 20°C in the absence of stress concentrations; with an Izod notch, the
impact strength is 48 Jm -1. This plastic possesses outstanding loadbearing
properties at normal and elevated temperatures.
Polyethersulphones can be used for tens of thousands of hours at 200°C
without significant loss in strength, a property which is the basis for a number
of applications, including internally illuminated push-button switches and
indicator lights for cookers. This excellent stability at high temperatures is not
matched by ultraviolet resistance in weathering, which is poor. However,
resistance to ionizing radiations, ([3-, "1- and X-ray) is good in the temperature
range 20-200°C. Polyethersulphone is a highly polar aromatic polymer, thus,
as expected, it is resistant to aqueous acids, bases and most salts and to
hydrocarbons, including petrol, oils and greases, even at high temperatures,
where glass-filled grades are recommended. A typical application is in the inlet
manifold between carburettor and cylinder in a petrol-engined power chain-
saw. Polar solvents, particularly of an aromatic type, are liable to dissolve
polyethersulphone partially or completely. In the presence of residual or
externally applied stresses, polar solvents will also give rise to crazing.
Figure 9.7 Polyethersulphone: element housing that locates the heater element of Anda high
speed hand drier, moulded by Wells and Hingley Ltd., Catford. Photograph by courtesy of leI
Ltd
Figure 9.8 Polyethersulphone integrated circuit socket developed and moulded by Jermyn
Industries Ltd .• Sevenoaks
Polyethersulphone is used in the heater element holder of a high-speed hand

drier (Figure 9.7). This unit has to endure a working temperature of 100°C,
with peaking temperature under fault conditions of 200°C, or even higher.
Polyethersulphone is eminently suitable for these temperature conditions and,
since it is unlikely to encounter solvents in this application, it would be
expected to have a very long service life. The part can be manufactured by
injection moulding on conventional equipment and has in fact, proved
successful in service. The non-flammability of the polymer is relevant in this
application, a characteristic leading to its use in aerospace applications where
cost considerations are minor compared to safety factors. A further attribute
of polyethersulphone is its ability to be shaped to fine tolerances, which is also
dependent on its inherent dimensional stability. An application illustrative of
this property is as a base fitting for integrated circuits (see Figure 9.8).
9.3 Poly(phenylene sulphide), (PPS)

Poly(phenylene sulphide) has a symmetrical repeat unit consisting alternately
of sulphide links and para-phenylene groups, so it is not surprising that this is a
crystallizable plastic.
The melting point, 277°C, is not particularly high, considering the

predominance of the aromatic groups in the structure (compared with
polyamide 6.6 with T m = 265°C). The T g of the polymer (88°C) is marginally
higher than that of poly(ethylene terephthalate), 70°C, suggesting that some
problems might arise in processing if rapid chilling is imposed. Quenching
does indeed affect the crystallinity significantly, as shown in Figure 9.9, which
depicts the flexural modulus of 'annealed' and 'as-moulded' specimens of
15
1-----_
temperature ("C)
Figure 9.9 Flexural modulus vs. temperature for 'as moulded' and 'annealed', 40% glass fibre-
filled PPS
SPECIALITY THERMOPLASTICS 14S
poly(phenylene sulphide) containing 40% glass fibre. Unfilled PPS is not
important commercially, the significant materials being those containing glass
fibre or combinations of glass fibre and mineral fillers; the latter compounds
require drying prior to processing because of the poor hydrolytic stability at
process temperatures.
Processing is usually by injection moulding for which the melt temperature
is 31S-360°C. Mould temperatures of SO-160°C have been used, although
temperatures above 130°C are preferred, giving increased crystallinity, better
dimensional stability at elevated temperatures, and improved gloss. High filler
content gives rise to low mould shrinkage (0.2-0.6%) for a crystallizable
polymer.
PPS has been called 'the poor man's polysulphone' because of its relative
cheapness; this refers to some similarity in properties between the polymers,
particularly temperature resistance. There is a significant change in the
mechanical properties of PPS, as shown in Figure 9.9, associated with a glass
transition temperature below 100°C, a phenomenon which does not occur
with polysulphones. The resistance of PPS to high-energy ionizing radiations
is excellent, probably surpassing that of polysulphones. However, its poor
resistance to UV radiation encountered in weathering is similar to that of
polysulphones: fortunately this behaviour can be markedly improved by the
addition of stabilizers. On the other hand, the chemical resistance of PPS is
inferior to that of the polysulphones, particularly to oxidizing solutions,
chlorine and chlorinated hydrocarbons and amines, although PPS is a
crystalline plastic. It may be inferred that the sulphide linkage, (-S-) is not
as chemically inert as is the sulphone group (-S02-)'
An outstanding characteristic of PPS is its resistance to fire. It is self-
extinguishing (having a critical oxygen index of SO), although if a flame is
present PPS will burn, charring without dripping or fire-spread. At the same
time, some smoke may be formed, but the concentration of potentially toxic
gases (e.g. carbon monoxide and mercaptans) is low.
Typifying the use of PPS is the handle of a carpet-bonding iron (see
Figure 9.10a). A similarity between cross-linked phenolics and poly(phenylene
sulphide) is that both can withstand operating temperatures up to 2S0°C:
Table 9.1 reproduces some of their properties.
These two materials differ considerably in mechanical properties, however:
the cheaper phenolics have much lower tensile strength, along with low tensile
elongation (O.S%). Both have good electrical properties and will withstand
direct contact with metal at 2S0°C. The main reason behind the choice of
specific materials for these applications is the design of each part. The design
with the open end (see Figure 9.10a) will have to withstand large flexural
stresses at its corners. Also, if any impact loads on the cantilever end will
induce large stresses in the component. Poly(phenylene sulphide) is therefore
suited for this application because of its excellent mechanical properties and its
suitability for operating at high temperatures (up to 250°C): by contrast,
Figure 9.10 Designs of handles for irons: (a) poly(phenylene sulphide) (Roberts Consolidated
Industries, California) (b) phenol-formaldehyde (Healey Mouldings, Oldbury)
Table 9.1: Properties of poly(phenylene sulphide) and cross-linked phenolics
PPS Phenolics
Cost High Low

Tensile strength 140 MPa at lOO°C 50 MPa at 20°C
20 MPa at 240°C 20 MPa at 250°C
Flexural modulus 12 GPa at lOO°C 21 GPa at 20°C
3 GPa at 250°C
Impact strength 80J,m- 1 at 2lOoC 20J,m- 1 at 20°C
Deflection temperature 260°C 182°C
phenol-formaldehyde lacks the strength. Another feature in favour of the PPS
is its high impact strength, which could be significant for equipment designed
for industrial use. The enclosed handle (see Figure 9.10 b), has smaller bending
moments at its corners when in use and so the stresses will be less. Furthermore
the 'integrity' of the design means that it is inherently much stronger. Therefore
both materials could be used in this application; however, the much cheaper
phenolic is chosen since it will operate adequately under the applied stresses.
The designer's task is to produce an attractive and useful product at an
economical price. In designing the irons, one designer has tried to change the
concept of the iron by adopting a cantilever shape, which should be technically
more satisfactory in use. By doing so, employing a higher-cost material has
resulted in a more expensive product. Nevertheless, the manufacturer has
decided that a more attractive product with a price disadvantage would be
more marketable than an iron with a more traditional design.
10 Cross-linked plastics
10.1 Introduction
A number of useful cross-linkable or thermosetting plastics are available.
When cross-linked, these materials tend to be stiff, but with poor impact
strength and low elongation. Normally reinforcing fillers have to be in-
corporated into the polymers to produce strong, useful materials, known as
composites. Selected fillers can be also used to enhance electrical properties,
such as volume resistivity, or to reduce the cost of the compounded polymers.
Cross-linked polymers used in large volumes include:
(i) Phenol-formaldehydes (PF), including the novolak moulding powders and
resolliquid impregnation resins
(ii) Amino-formaldehydes, including urea-formaldehydes (UF) and melamine
formaldehydes (MF), (also known as amino-plasts)
(iii) Unsaturated polyesters, glass-fibre impregnation resins, dough-moulding
and sheet-moulding compounds (DMC and SMC respectively), and
moulding powders
(iv) Epoxide resins, normally available as liquid impregnation resins.
Other thermosetting materials are used in relatively small quantities in
specialist applications, including alkyd and silicon resins; polyurethane resins
are discussed in the next chapter.
Thermosets differ fundamentally from the thermoplastics in many respects.
To form a cross-linked polymer, the reactants used will have functionalities
greater than two. It is important to note that the shaping stage is associated
with chemical change in the system. Since chemical reaction is inevitable in
processing, the opportunity can be taken to reduce many of the difficulties
found with thermoplastics shaping. In particular, the very high melt viscosity
inherent with thermoplastics is avoided by working with comparatively low
molecular weights and reactive prepolymers (or oligomers). Prepolymers
exhibit certain thermoplastic characteristics, but will melt at relatively low
temperatures to give low-viscosity liquids-some are mobile liquids at room
temperature, or are made so by the use of solvents, such as unsaturated
polyesters dissolved in styrene. With a few exceptions, very high-pressure
moulding equipment is not required, and shaping of thermosetting materials
can be accomplished on relatively low-cost equipment. Accurate proportion-
ing and mixing equipment is needed to handle dual-component systems.
CROSS-LINKED PLASTICS 149
Fillers may have a marked effect on the flow properties of these materials.
As processing is associated with chemical changes in the polymer, there are
several interactions of the prepolymer with the shaping operation. Prepoly-
mers can either react with themselves, or by addition of a reactive cross-linking
or curing agent. The reaction proceeds initially by chain extension with an
increase in molecular weight, and then cross-linking to form a three-
dimensional network system, which will eventually, in theory, have an infinite
molecular weight. Both addition of catalysts and increasing the temperature of
the reactants will increase the reaction rate. So, in any process, heating to effect
melting and flow must not bring on premature cross-linking before shaping is
complete. As the chemical changes are associated with increased molecular
order, appreciable shrinkage frequently occurs on curing. In practice, this can
be reduced by the incorporation of fillers, or of shrink or low-profile additives:
these are discussed in detail in section 10.5.
A difference between the shaping of thermoplastics and that of thermosett-
ing plastics is that the time-dominant cooling stage necessary to stabilize the
shape of a thermoplastic component is replaced by the time-dominating cross-
linking reaction taking place in a hot mould or press. Furthermore, while it is
good practice in thermoplastics injection moulding to maintain approxi-
mately constant cross-sectional areas, and preferably constant thickness in the
flow path, such restrictions are not so important for thermoset moulding.
There are two more advantages of thermosetting plastics. First, the absence
of post-moulding shrinkage ensures that very close tolerances can be held,
leading to acceptance for precision mouldings. Second, the low viscosity of the
pre polymer at the shaping stage means that gates in injection moulds can be
positioned as convenient, without so much consideration of features such as
weld lines (although highly-filled compounds can cause problems).
10.2 Phenol-formaldehyde plastics

Phenol-formaldehyde (PF) resins were the first man-made plastics to be used,
being first exploited commercially in 1910. Early applications were in the
electrical industry where much of the development and manufacture was
accomplished.
Phenol is a petrochemical derived from benzene and propylene by the
cumene route, and formaldehyde is obtained by the oxidation of methanol
which in turn is derived from synthesis gas. Until the 1950s, phenol, as
extracted from coal tar by distillation, was contaminated with cresols and
xylenols.
The PF prepolymers may be of two types, the novolaks and resols. The
novolaks are prepared from excess phenol and formaldehyde (in the molar
ratio 5:4) under acidic conditions. The monomers react slowly to form 0- and
p-methylol phenols (Reaction 1), which then condense rapidly with further
phenol to give dihydroxyl diphenyl methane types (Reaction 2):
HCHO - - ¢ C H20 H
Reaction 1
oH
6 --
Reaction 2
Of the three isomers, 2.4' and 4.4' predominate. These then react to form
methylol derivatives which in turn react with more phenol to give polynuclear
phenols. Stoichiometry demands that the reaction stops when there are
approximately five benzene groups per molecule (Reaction 3):
6¥
OH
HO-oCH2Q-OH
A-CH2
CH2
~CH2-o0H
H0
Reaction 3
The resulting novolak resins do not contain reactive methylol groups and so
will not self-cross-link on heating. Instead, novolaks are compounded with
reactants capable offorming methylene bridges at elevated cure temperatures
and usually under alkaline conditions, e.g. hexamethylene tetramine ('hex a'),
or paraform. A novolak resin is predominantly tri-functional, being open to
cross-link formation at the 0- and p-positions.
A resol is formed by reacting a phenol with excess offormaldehyde (phenol
to formaldehyde ratio up to 1:2.5), normally under basic conditions. Phenol
alcohols are formed rapidly, but their subsequent condensation is slow: thus
there is a tendency for a mixture of phenol alcohols and methylols to be formed
(Reaction 4). Heating of the resins will cause cross-linking via methylol groups
or more complex routes. Novolaks and resols are soluble and fusible low-
molecular-weight products, and cross-linking can be effected at temperatures
below 160°C, occurring via the -CH2-and-CH2-0-CH2-bridges.
Above 160°C, quinone methides are formed (Reaction 5): these are conjugated
double bond systems and account for the dark colour of PF plastics.
OH OH
HO H,C -o-CH'VCH ,OC H'OC
C H2 0 H
Reaction 4
Reaction 5
Condensation products will be evolved during the cross-linking reactions and

it is still a matter of debate what happens to them. It is assumed that, under the
moulding conditions employed, they will form solid solutions in the cross-
linked resin.
10.2.1 Novolak PF resins

Moulding powders are usually based on novolaks and 'hexa'.1t is necessary to
incorporate fillers to lower the resin content and reduce the shrinkage. Wood-
flour is commonly used to improve impact strength and as a cheapener. For
better impact strength, fibrous fillers (cotton flock, chopped fabric) are used;
mica and asbestos are employed to give the best electrical properties.
Improved strength is derived from covalent bonding at the interface between
the PF resin and the cellulosic fillers. Curing is carried out at high
temperatures for short cycle times, although dark products result.
Bulk applications of PF resins utilize novolaks in formulations designed for
rapid cure. Traditionally, components were manufactured by compression or
transfer moulding, the latter being preferred for products with moulded-in
inserts. Injection moulding is gaining in use, for example for electrical
components, electric iron handles (see Chapter 9), or saucepan handles (see
below).
Since the final polymer is cross-linked and highly interlocked, phenolic
mouldings are hard, insoluble, heat-resistant materials. Chemical resistance
depends on filler and resin; PFs are attacked by caustic soda solution, but
plastics based on cresols and xylenols are more stable. They are resistant to
many acids except formic and oxidizing acids. Electrical properties are not
outstanding, but are adequate for many insulation purposes. Compared to the
amino-plastics, PFs have poor tracking resistance.
PF mouldings are still widely employed, for example for knobs, handles,
instrument cases, bottle caps and closures. Although still used in some
electrical equipment, particularly where heat- and moisture-resistance are
important, PF has been largely superseded by urea- or melamine-
formaldehyde, unsaturated polyester or epoxide resin in plugs and switches.
PF is used in several automotive applications. It is still dominant in distributor
heads and ventilation systems where good long-term heat resistance in a
hostile environment is required: there is some competition from some of the
higher-temperature-resistant engineering thermoplastics. Asbestos-filled
grades are used in brake-shoes and exhaust heat shielding.
Saucepan handles are common components found in everyday use, for
which plastics are eminently suitable in respect of their low thermal
conductivity. Plastics can be easily shaped to complex sections which allow
safer handling by providing a surer grip. Mechanical property requirements
are very demanding because of the danger of failure in service, which could
subject the user to scalding or worse. For example, a danger with a gas hob is
that a flame can extend up the outside of the pan, subjecting the handle to
softening heat, the possibility of ignition, and cracking with loss of mechanical
strength. PF moulding materials have high rigidity and mechanical stability at
high temperature coupled with flame resistance and low cost; in addition, the
polymer can be cost-effectively injection moulded in large numbers (Figure
10.1 ).
Two examples of applications involving mechanical and electrical pro-
perties are the brush box moulding and a component of a multi-function
electrical switch. The brush box moulding is a component of an electrical
starter motor manufactured by Lucas Electrical Ltd. (Figure 10.2). The main
purpose of the moulding is to locate and position the carbon bushes which
make contact with the slip ring on the motor armature shaft. In order for the
motor to operate efficiently, exacting tolerances are required in the position
and the shape of the brush locations. Further, the product has to withstand
localized hot spots in the areas around the brushes and must have good
electrical properties.
The material chosen for this application was a short-fibre asbestos-filled
phenolic because of its good electrical properties, resistance to localized high
temperatures and close post-moulding dimensions which are achieved with
very little moulding distortion. Originally the components were made using
compression moulding in a four-cavity mould. The overall cycle time was 165
seconds, of which 120 seconds was the cure time. However, difficulties were
experienced because the tool design was complex, and flow problems occurred
using pre-heated pellets. If the pre-heated pellets were too hot when placed
Figure 10.1 Sculptured saucepan handles injection-moulded by Healey Mouldings Ltd, Oldbury,
in phenol-formaldehyde compound
Figure 10.2 Brush box injection moulded by Lucas Electrical Ltd, from asbestos-filled phenol-
formaldehyde
into the mould cavity, the PF would cure prematurely, producing discontinu-
ity in the moulding; if too cold, the pellets would exert excessive force on the
thinner sections of the mould, causing distortion.
As a result of the necessity to maintain and repair the compression moulds,
injection moulding was considered as an alternative. The initial mould was
II III
~
"'o
""'
>
time, temperature
Figure 10.3 Flow-cure relationship for a typical phenol-formaldehyde moulding compound

I Plasticization period
II Injection stage
III Curing process
designed using a three-plate concept, with a central feed supplying two

cavities. Special attention was paid to the design of the runners, to ensure that
the sprue and runners were separated from the moulding when the mould was
opened. Injection moulding of thermosets requires accurate control of the
moulding parameters, temperature, pressure, time and screw rotation speed,
because of the flow behaviour of these materials. It is therefore necessary to
understand the interrelationship between changes in viscosity with time and
temperature (Figure 10.3). When the material is injected into the cavity it is
essential that its viscosity is at a minimum to permit easy flow. Adjustments to
the injection speed and barrel temperatures can be made until optimum
mouldings are obtained, then the cure time can be reduced; the cure time will
be the minimum time in which mouldings can be produced, without blistering
or distortion.
During proving trials using injection moulding equipment with a suitable
PF moulding powder, the minimum cure time was established at 45 seconds
with an overall cycle time of 58 seconds. As a general rule, injection moulding
of thermosets is much quicker than compression moulding because the
material is much further advanced into its cure when the cavity is filled. In this
example, a single injection moulding machine using two cavities would
produce 42% more throughput than single compression moulding press with
four cavities. However, this improvement has to be offset against the increase
in waste material produced as sprue and runners; the overall shot weight was
43.5 g against the original 30.5 g by compression moulding. To reduce this
wastage, warm runners were considered, but further difficulties were met: the
mould had to be kept at the cure temperature (160-180°C) and the runners at
the plasticizing temperature (60-80°C). Initially the runners restricted the
flow, but satisfactory mouldings were produced by increasing their cross-
sectional area. Ideally, the shot weight should equal the trimmed moulding
weight, which is difficult to achieve in practice. However, after proving trials,
nylon pivot piece
phenolic base
moulding
Figure 10.4 Phenolic component in a multi-function switch for motor vehicles manufactured by
Lucas Electrical Ltd
a stalk 20 mm long remained connected to the moulding, with the final

and acceptable shot weight of 34.5 g.
The base moulding shown in Figure 10.4 is a component of a column-
mounted multi-function switch used in motor vehicles to operate the direction
indicators and horns, and to select main or dip beam. The base is required to
bolt to the steering column, to locate the rotor and act as a bearing for the
rotation of the rotor, while holding the contacts for the switching of the
direction indicators.
The first prototypes were made with both base and rotor made from
polyacetal. The unlubricated acetal mating surfaces ofthe switch 'squeaked' in
operation, giving rise to an undesirable and annoying side effect. Lubrication
was not acceptable because of the close proximity to the electrical contacts.
The alternatives were either to place another material between the rubbing
surfaces, or to change the polymer. A polyamide washer was tried and,
although successful, was found not to be cost-effective. Instead the base was
made in PF, offering a cheap and simple replacement to acetal. The PF
allowed a design which incorporated thin and thick rigid sections, to a much
greater extent than any thermoplastic. The base was redesigned with thick
sections to give strength and rigidity.
However, a problem arose in service with the PF base after it had performed
several thousand operations. In the operation of the switch, a metal electrical
contact was forced along a ramp to make contact with a second conductor, the
mating contacts being preloaded on contact. Unfortunately the moving
contact rubbed away a small amount of material from the surface of the ramp,
which became built up around the contacts, and after long use the switch
would become inoperative. This was corrected by moving the ramp away from
the electrical contacts so that when the mating contact rubbed itself along the
ramp, the loosened material would be away from the contact.
The replacement phenolic base was originally compression-moulded in a

two-cavity mould with a cycle time of 70 seconds at a moulding temperature of
155 ± 5°C. After the introduction of direct screw injection feed into the
compression mould, the cycle time for the component was reduced to 52
seconds.
10.2.2 Resol PF resins

Until the early 1980s, resol resins were only used in large volumes for
production of paper and fabric laminates. Resols are readily soluble in water
and aqueous alcohol solutions, allowing ease of impregnation of paper and
many other fibrous materials. After impregnation, the material is dried at 80-
100°C to remove the solvent without inducing cross-linking. Flat laminates
are formed by plying up layers (or foils) of impregnated paper in a heated press.
Decorative laminates (e.g. Formica™ types), include a top layer of water-
white MF impregnating printed paper and a barrier layer of thin-gauge
aluminium foil. The aluminium is employed to prevent strike-through by the
dark-coloured PF used in the core, to promote heat transfer and minimize
local distortion in the finished product, for instance if a hot saucepan is placed
on a work surface. If a cigarette is allowed to smoulder, the interlayer of foil
will aid heat transfer and will help reduce burn marking, PF and MF having
good flame resistance. Paper laminates are widely used in the electrical
industry. Thick paper and cotton fabric laminates find application as very
durable gear wheels (e.g. Tufnol™ products), although a gear wheel will have
to be machined from block, rather than being moulded semi-finished.
PF foams based on acid-cure resol resins and blown using physical blowing
agents (n-alkanes or fluorocarbons) find use in specific applications. Origin-
ally, PF foam oflow density (20-100 kg m - 3) suffered from the problems of
high friability and open cell structure, limiting its use as an insulation material.
Development of surfactants to stabilize cell structure during blowing and cure
has given rise to a closed-cell material whose insulation characteristics (based
on thermal conductivity data) are as good as polyurethanes at similar
densities, and appear to be retained for longer (Table 10.1). Most importantly,
the PF foam provides very low flammability and smoke emission in cellular
boardstock material, having no competition in fire-critical applications.
An open-cell hydrophilic grade of PF foam is used in floristry to increase the
life of cut flowers. The foam will readily absorb a large volume of water, while
supporting flower stems pushed into it (an example is Oasis™).
Sprayable grades of PF foam are being developed for in-situ use (for
example as replacement for asbestos in building applications), curing within
one minute, although reaction between the mixed ingredients (PF resol plus
strong acid catalyst) can be neutralized by alkaline substrates such as concrete
unless primer coats are first used. The fire properties of PF foams can be
affected by choice of acid catalyst and blowing agent.
Table 10.1 Thermal conductivity of phenol formaldehyde
insulation foam. By permission of Kooltherm Ltd
Thermal Conductivity (W m - 1 K - 1)
Age Parallel* Perpendicular*
o 0.0178 0.0176
30 days 0.0158 0.0143
19 weeks 0.0163 0.0148
11 months 0.0170 0.0155
23 months 0.0186 0.0166
35 months 0.0206 0.0181
48 months 0.0214 0.0189
(1) Testing ofBS 874: 1973 (1980), Appendix B: Heat-flow Meter.

Testing at a mean temperature of 10°C, storage temperature of
21°e.
(2) *Unfaced cut samples taken from parallel and perpendicular
direction to original rise.
(3) PF foam based on Cello bond KTM (BP), nominal density
35 kgm - 3, mixed fluorocarbons used as blowing agents.
(4) Laminated insulation board maintains a lower value of
thermal conductivity for longer than the unfaced material, i.e.
superior retention offluorocarbons in the foam's cell structure.
(5) Thermal conductivity values (W m -1 K -1) for other insul-
ation materials;
Rigid PU (35kgm- 3 ) 0.018 (initial and 0.023
after short -term ageing).
Expanded polystyrene
(16kgm- 3 ) 0.031
Glass wool (64 kg m - 3) 0.036
Expanded PVC (40kgm- 3 ) 0.030 (after Brydson, ref. 4)
Intregral-skin PF foam is being produced by reaction injection moulding

techniques, for specialist products such as one-piece drop-down tables for
passenger aircraft.
The importance of the fire resistance, combined with low smoke emission, is
now leading to the use of PF as a replacement for unsaturated polyester sheet
in many glass-fibre-reinforced products. London Transport Underground
service specifies PF sheet moulding compounds (PF.SMC), to the exclusion of
polyester,.in the manufacture of passenger seating (see also Figure 10.5). It has
been necessary to develop new grades of glass fibre compatible with PF and
new thickening agents (based on isocyanates for example), giving a material
that will process like the polyester SMC and at relatively low temperatures.
Glass-reinforced PF composites are made by hand lay-up techniques;
examples of potential use include the weapons and equipment storage boxes
used on British naval ships, where, following the Falklands conflict, fire
retardancy and low smoke emission were found to be essential. Unfortunately,
the strength of acid catalysts employed with the earlier commercial systems
has caused handling and mould corrosion problems in both PF hand lay-up
and PF.SMC applications. Alkali-cure PF systems seem to have overcome
this problem, but have to be processed at higher temperatures.
Figure 10.5 An example of the strength combined with excellent fire resistance properties of glass
reinforced PF: whole front end of the London Underground 'C' train. By permission of London
Transport Ltd and BP Chemicals
With the recent introduction of PF foams and SMC materials, the

application of phenolics appear to be having a renaissance, and perhaps they
will regain some of their market share of 30 years ago.
10.3 Urea-formaldehyde plastics

Urea-formaldehyde (UF) and melamine-formaldehydes are known as the
aminoplasts. Interest lies in UF, since it is based on intermediates not derived
from oil, and therefore price escalation is less of a problem than for most other
plastics.
Urea is obtained by reacting carbon dioxide and ammonia, the ammonium
carbamate formed being dehydrated to urea (Reaction 6):
C02 + 2 N H3 -- N H 2 C 0.0 N H 4 -
N H 2 CO. N H 2 + H20
Reaction 6
Urea and formaldehyde react to form mono- and dimethylol ureas, which are
the usual prepolymers for UF plastics (Reaction 7):
O=C/ NH2 + H.CHO _

'N H2
+ 0= C/ N H. C H2 0 H
"NH.C H2 0 H
Reaction 7
Cross-linking is brought about by any of a number of mechanisms (Reactions

8, 9 and 10):
+
rvN H.C H20 C H2.N H"-'

! +
H.C H 0
Reaction 8: Methylol-methylol condensation
Reaction 9: Methylol-imino reaction
+ H.C H 0
--
Reaction 10: Formaldehyde-imino condensation
UF plastics find widespread use because of their low cost and the possibility of
pigmenting in a wide colour range, including pastel shades, not possible with
PF materials. They have poorer water and heat resistance than PFs, only
operating up to 70°C, although this can be improved by modifying with

melamine. Notable properties of the UFs are the good electrical resistance,
including resistance to 'tracking' - degradation of the polymer by electrical
breakdown which leaves a conducting 'track' on the surface. This is important
in electrical plugs and sockets. Foodstuffs are not tainted by UF, and so it can
be used for caps and closures; good resistance to glycol and alcohol also
promotes the plastic's use in these applications. UF is favoured in the use for
caps and closures, especially for its 'feel' of the component and its visual
appeal. Technically UF provides products which are strong and rigid, and
reasonably immune to attack by a wide variety offluids, which in turn will not
be contaminated by the plastic. Figure 10.6 shows a selection of metallized UF
closures.
Wood-flour is normally used as a filler, except for very light colours where
the purer a-cellulose is employed. The bulk ofUF mouldings are found in caps
and closures of bottles and other containers, and in electrical fittings.
Substantial quantities are still used in applications as diverse as buttons and
toilet seats. UF resins are used as wood adhesives in the manufacture of
plywood and chipboard. Acid-catalysed UF foams (U-foam) are used to fill
cavity walls on site, competing successfully against PUs, PFs and mineral
wools, UF foam is a highly-closed cell system at densities less than 10 kg m - 3,
Figure 10.6 Caps and closures moulded by Metal Closures Mouldings Ltd from urea-
formaldehyde moulding powder supplied by BP Chemicals Division and subsequently metallized
but because it is very friable, use is limited, needing the protection of the double
layer of cavity brick wall to prevent rapid mechanical breakdown. Foams are
also used as firelighters.
10.4 Melamine-formaldehyde plastics

Melamine is obtained from calcium cyanamide via dicyandiamide by a
sequence of reactions (Reaction 11);
- - NH2·C.NH.CN
II
N H
Reaction 11
Melamine and formaldehyde react to yield methylol-melamines, the degree of

methylolation depending on the melamine/formaldehyde ratio. The principal
cross-linking reaction involves methylol-methylol condensation to -CH 2 -
O-CH 2 - , although methylene links may be formed by the elimination of
formaldehyde from the bridge or by methylol-amine condensation, the first
two reactions being similar to those of UF prepolymer's cross-linking
mechanisms.
Melamine-formaldehyde (MF) mouldings compare favourably with their
UF counterparts in all properties. The plastic has better heat resistance, lower
water absorption, better stain resistance and higher hardness and abrasion
resistance, but its price is higher.
An important application is in tableware (Figure 10.7), picnicware and,
more recently, kitchenware (Figure 10.8), in all of which tactile and aesthetic
properties are important along with good mechanical and chemical pro-
perties. MF is used to impregnate the surface lamination of decorative
laminates, to give an attractive product of very high hardness, such as
Formica™ and Warerite™ types. Glass-reinforced MF laminates are used in
good-quality electric boards, having heat resistance to 200°C and good
electrical properties, including tracking resistance.
Figure 10.7 Melamine moulding powders are used for this range of tableware
Figure 10.8 Melamine moulding powders are used by Addis for its range of kitchenware
10.5 Unsaturated polyester resins
There are many different types of hydroxylated and dicarboxylic acid
monomers that will react and form ester linkages. In section 7.3, the saturated
thermoplastic polyesters such as poly(ethylene terephthalate) were considered,
and materials such as poly(propylene adipate) are used as plasticizers for PVc.
It should be noted that polymers with the ester grouping in their side chains,
such as poly(vinyl acetate) or poly(methyl methacrylate), are not classified as
polyesters. Variation of the starting monomers permits a limited choice of
properties to be built into the structure of the final polymer.
An unsaturated dicarboxylic acid provides two types offunctionality. It can
be partially polymerized by a step-growth condensation reaction with a glycol,
(in non-stoichiometric proportions) to yield a polyester oligomer or pre-
polymer with residual unsaturation in its chain. The unsaturation can be
reacted at some later stage, by free radical initiators permitting a limited chain
reaction with a low-molecular-weight unsaturated monomer (styrene, for
instance, being a common cross-linking agent). There are usually three
constituents in the prepolymer:
(i) Glycol, frequently propylene glycol (propane-I,2-diol) to prevent the
polyester crystallizing by steric hindrance (cf. ethylene glycol)
(ii) Saturated acid to reduce the degree of cross-linking, usually either one of
the phthalic isomers, or adipic or sebacic acids if flexibility is required
(iii) Unsaturated acid, which is always maleic acid (or maleic anhydride) or its
trans isomer, fumaric acid.
Normally the unsaturated acid/saturated acid ratio is between 1: 1 and 2: 1.
Polyesterification is appropriate to the acid mixture employed and is carried
out to a molecular weight of about a thousand. The resulting resin is extremely
viscous, if not solid, at room temperature and must be diluted with a liquid
vinyl monomer, either styrene or a styrene/methyl methacrylate mixture,
which will subsequently participate in the cross-linking reaction. For isoph-
thalic and terephthalic acid-based systems, polyesterification is usually carried
out in two stages. First, the saturated phthalic acid is reacted with glycol to
produce a very low-molecular-weight polyester chain with hydroxyl termin-
ation (called tipping). In the second stage, this product is treated with
unsaturated acid (or anhydride) to yield the unsaturated polyster oligomer;
this is dissolved in styrene. The mixture is usually a pale amber, syrupy liquid
and contains inhibitors to prevent premature cross-linking. Quality control
tests include density, viscosity, acid number and colour.
The cross-linking reaction is initiated by peroxide catalyst at SO-IS0°C, or
by a redox system at room temperature. Initiators include benzoyl peroxide
and t-butyl perbenzoate for high-temperature curing, or methylethylketone
peroxide and cyclohexanone peroxide, with cobalt octoate or naphthenate as
accelerator for low-temperature processes. Photo-initiators are used in thin

film applications, such as UV curable surface coatings.
10.5.1 Structure and properties

The cross-linked unsaturated polyester resin (UPR) is a rigid product, but its
detailed microstructure is less well defined. If maleic acid is used in the
condensation reaction, most of it isomerizes to the more favoured trans-isomer
(fumarate), which reacts differently with styrene, as shown by the different
copolymerization reactivity ratios in 'model' reactions (Table 10.2). The data
show that in the styrene/maleate system, the styrene is more likely to
homopolymerize; this is clearly undesirable when employed for cross-linking.
The styrene/fumarate reaction is more favoured for copolymerization and
hence for cross-linking.
The uncertainty of the maleate/fumarate ratio in any polyester oligomer, may
account for reactivity differences in UPR, since reaction rates are also
different. Cross-linking density can be adjusted by varying the
unsaturated/saturated acid ratio, and the rigidity can be increased by going
from an aliphatic to aromatic acid. Ester groups provide sites for hydrolytic
degradation, particularly in alkaline conditions, limiting the use of simple
resins in corrosive environments. This has lead to the development of a wide
variety of cross-linked plastics with superior hydrolytic stability. This
property can be improved by replacing ortho-phthalic acid by the meta- or
para-isomers, isophthalic and terephthalic acid respectively. Further improve-
ments can be obtained by more extreme changes in the chemistry, such as in
the vinyl ester resins, although these products are considerably more expensive
than the conventional UPR. The structure of the polyester, especially after
reacting with styrene, promotes poor fire resistance. External fire retardants,
such as halogenated phosphorus compounds or antimony trioxide have to be
used in the event of fire risk; alternatively, chlorinated dicarboxylic acids can
be used in the synthesis of the unsaturated polyester chain.
10.5.2 Glass fibre-reinforced polyesters (GRP)

UPRs are normally rigid, brittle materials and as such cannot be used alone to
form moulded products. Instead the polyester has to be reinforced with fibrous
material having a tensile modulus at least ten times that of the cured resin: the
resin may be considered as an adhesive matrix binding the fibres together.
Table 10.2 Reactivity ratios of styrene with unsaturated ester groups
Styrene/diethy! maleate Styrene/die thy! fumarate
6.52 0.3
0.005 0.07
Glass fibre is a preferred form of reinforcement, providing strong laminates
at an economical price. Several forms are important. Glass cloth is expensive
and will only be used for the most critical applications: various weaves are
available. Chopped strand mat consists of bundles of glass filaments,
approximately 50 mm long, bonded by a resinous binder. Other forms of glass
fibre including needle mat, rovings, yarns, tapes, surfacing mats and conti-
nuous filaments are available. Short-length hammer-milled and chopped
strand fibres (0.2 to 5 mm) are also used in special products. The glass may be of
two types; E glass, a low-alkali borosilicate for electrical applications, and
A glass, a cheaper variety for general use, with an alkali content of 10-15%.
It is usually necessary to provide a finish for the fibres to facilitate good
wetting and interfacial bonding between the glass and the resin. Most
important is vinyl trichlorsilane treatment, which gives direct chemical
linkage between glass and resin:
HO C H=C H2
'51'
/ \.
o 0
l,....r I
~ Si ,..JSi'"'f
( (
Binder materials for chopped strand mats include starch, poly(vinyl acetate)
and polyesters. It is important that the binder is compatible with the resin and
the end-use of the laminate. In the production of glass/resin composites,
several rules must be obeyed to achieve optimum mechanical properties.
These include maximum glass-to-resin ratio and the establishment of good
wetting and air release in the composite's structure.
The chief process for manufacturing large structures is the hand lay-up
technique. The method allows large structures to be made without com-
plicated moulds; the resulting product has superior heat resistance compared
to many thermoplastics, and the strength and rigidity are good (2-10 times
better than most thermoplastics), at densities less than that of most metals
(1.4-2.2 Mg m - 3).
There have been many attempts to reduce the very high labour content of
the hand lay-up technique, and similar efforts to reduce the cost of the
materials involved. An important attribute of the process is that the
reinforcing fibres can be used very effectively by disposing them geometrically
to counter the greatest stresses in use. This is unlike many other moulding
processes where there is a risk of undesirable fibre orientation. It should be
noted that maximum interlaminar strength is achieved by laying-up sub-
sequent laminates while the substrate is in a near gel state but still has a tacky
and therefore active surface. Ideally, there should be limited interpenetration
of fibre across the interface without any major disturbance of the rest of the
glass fibre.
Figure 10.9 Arun class lifeboat in GRP under construction
Figure 10.10 Hand lay-up of polyester GRP, used in the production of panels for exterior kiosks.
By permission of WES Plastics Ltd
Examples of the strength, durability and potential size of polyester
laminates can be found in the marine field, e.g. in the construction of boats and
ships: notable examples are the 'Arun' class lifeboat in service with the Royal
National Lifeboat Institution (Figure 10.9), and minesweepers in service with
the Royal Navy. Relative sizes are 17 and 60 m, the latter using 300 tonnes
ofUPR.
There is controversy as to whether spray-up methods give GRP laminates
as good as those obtained by hand lamination, but there is little doubt that the
products are adequate for many applications, including leisure craft. Figure
10.10 shows one stage in the production of panels used in the fabrication of
semi-permanent exterior kiosks. Gel coat can be spray-applied to the released
surface of the mould in a small fraction of the time taken by hand. This is then
followed by a mixture of glass fibres and catalysed resin, the former being
obtained by chopping 'continuous glass rovings' fed to the spray head.
Proponents of the technique claim that there are economies in time (cutting of
the chopped-strand mat to shape is eliminated and spray application is
claimed to be faster than brush and roller impregnation), and in cost (the
continuous rovings being cheaper than chopped-strand mat).
As an alternative to the 'bucket and brush' technique of resin impregnation
or spray application and their associated limitations in production control,
resin injection has been developed. A matched mould system capable of
withstanding high pressures has to be used, and so limits product size, the
largest commercial mouldings being produced are car bodies made in limited
numbers (e.g. Lotus cars). Another problem is that the viscosity of the resin
must be low and there is the operating problem of ensuring that the catalysed
resin does not gel in the injection unit. The advantages of resin injection
includes dimensional repeatability, maximizing glass/resin loading (60-80%
glass in the composite), air removal and the styrene liberated into the
atmosphere can be very much reduced and therefore contained.
For the methods of application above, resin viscosity must be maintained
low, and this precludes the use of particulate fillers as inert diluents to cheapen
the system. Sheet-moulding compound (SMC) and dough-moulding com-
pound (DMC) prepolymer forms ofUPR continue to be a major growth area
of GRP technology.
SMC is prepared by blending uncured UPR resin, with styrene, heat-
activated catalyst, inert particulate fillers, internal release agent and low
profile aids. In the final stage. of mixing, MgO or Mg(OH)2 is blended into the
paste. This compound will gradually react with the polyester, either by
hydrogen bonding or more probably by additional esterification. As a result,
the viscosity of the paste will increase within hours from 5 to 500 Pa s and the
material will be handleable, being essentially dry to the touch. The combin-
ation of the catalyst and the MgO thickener gives the UPR a short shelf-life,
normally less than 3 months. However, before the viscosity increases the resin
ble~ must be coated on to polyethylene or polyamide film (to facilitate
Table 10.3 Typical polyester SMC and DMC recipes
Weight (%)
SMC DMC
Polyester resin 30.0 25.0

Peroxide initiator 0.5 0.5
Calcium carbonate 33.5 45.5
Low shrink/profile additive 6.0 5.0
Release agent (e.g. zinc stearate) 2.0 2.0
Pigment 2.0 2.0
Thickener (e.g. MgO) 1.0
Chopped glass fibre 25.0 20.0
handling), chopped glass fibre (50 mm long) is randomly deposited on to the

resin and a second resin-coated film applied on top. The sandwich is
compacted between rollers to speed wetting of the glass and to give uniform
thickness to the sheet. The sheet is rolled up and allowed to mature at 40°C for
48 h. The final glass fibre loading will be 25-40% of the SMC. Typical
formulations of SMC and DMC are given in Table 10.3.
Solid thermoplastic polyester (melting at 80-90°C), has been used as an
alternative thickener to MgO. This material is claimed to increase the shelf-life
of the SMC considerably, but its 'melt viscosity' in processing is much lower
than the norm, leading to an increased risk of glass fibre/resin separation in
longer flow paths.
In moulding, the film is removed and the SMC cut for charging into the
mould: several plies can be built up for thicker moulding sections. The SMC is
shaped by press tools, heating causing initial flow and subsequent cross-
linking. The viscosity of the SMC is sufficiently high for the glass fibres to be
carried with the resin in the mould, but care has to be taken to prevent
excessive flow which will cause orientation in the fibres and in some in-
stances fibre dilution, producing weaknesses in the product. A further
consideration is that the charge shape should be obtainable without waste
from the SMC sheet available. Currently SMC use is limited by;
(i) Limited thickness of uncured stock, 10 mm being the maximum, although
this is not considered a real problem by vehicle manufacturers, for
example
(ii) The ability to predict flow patterns during shaping, particularly to reduce
weld-line failures
(iii) Design of blanks to give optimum properties
(iv) Surface defects, resulting from air traps blistering in post-moulding
operations. Low profile additives and in-mould coating techniques have
provided only limited relief from the defects. Usually costly and time
consuming post-moulding filling has to be carried out before a cured
SMC component can be painted.
Although, on mechanical property grounds, it is desirable to have restricted
flow (i.e. it is normal to have no more than 50% increase on the original charge
area), the surface finish of the moulding is improved by encouraging more flow,
that is by using a SMC charge of lower area and greater thickness. There is
some development of SMC as a lightweight load-bearing material. Polyester
SMC is used largely in the manufacture of semi-structural vehicle components,
particularly for body panels for truck cabs, car bonnets, roofs and fenders (see
Figure 11.9). Apart from automotive use, SMC finds application in building
(window frames, meter boxes); furniture (outside tables, chairs); and electrical
components (switch boxes, electrical cabinets, road-lamp housings, television
cabinets). Other large SMC units moulded in a single piece include satellite
receiving dishes, which are about 1 m in diameter (Figure 10.11). SMC is
normally transparent to many frequencies of radio-waves, and so has to be
surface coated with a special reflective paint to direct satellite signals to the
dish's receiver.
Dough moulding compounds (DMC) are prepared by blending resin, filler,
glass fibre (10-25 mm long), pigment and internal release agent in a dough
mixer; the resulting material has the consistency and handling characteristics
Figure 10.11 Domestic satellite receiving dish, based on polyester SMC. By permission of BTR
Permali Ltd
Figure 10.12 British Rail passenger seat frames moulded in DMC.Photograph: British Rail
of a bread dough. DMC can be compression- or injection-moulded, although

pressures required are low, 15-75 bar. Polyester DMC is popular for the
manufacture of mechanically strong electrical insulants, such as domestic plug
tops and sockets, now available in a variety of bright colours. It is also used to
mould large and strong articles such as passenger seat frames, for British Rail
(Figure 10.12).
The overall pattern of use of polyester GRP is given in Table 10.4.
Competition in the automotive industry is coming from phenolic and
thermoplastic SMC, and certain engineering thermoplastics.
10.6 Epoxide resins

In comparison to the polyester resins, epoxides have limited and specialist
use, and cost at least twice as much. However, they have superior toughness,
will operate at slightly higher temperatures, have excellent adhesion to many
substrates and are particularly resistant to alkaline environments. In parti-
cular, the chain extension and cross-linking reactions do not normally
Table 10.4 Uses of polyester GRP
Weight (%)
Building and construction 15

Land transport 26
Marine 22
Tanks, pipes, corrosion-resistant applications 10
Electrical 8
Other industrial 8
Other applications (e.g. consumer goods) 10
Aircraft 1
produce side products, and there is less shrinkage compared with other
thermosetting plastics. This allows mouldings of superior quality and
dimensional tolerance to be manufactured, especially in the gate area.
The most important epoxide resins are oligomers produced from the
reaction of bisphenol A and epichlorhydrin. Bisphenol A is prepared from
phenol and acetone, and need not be pure. Epichlorhydrin is made from
propylene via the hydro chlorination reaction with propylene oxide. Diglycidyl
ether is produced in the reaction of bisphenol A with excess epichlorhydrin
(2-3 times stoichiometry), in an alkaline solution to prevent higher homo-
logues being formed (n = 1. in Reaction 12).
o
......... "'-.
+ C H 2. C H . C H 2. Cl
! No. 0 H
oH CH3 0H
Cl.C H2.t H.CH20Q-? - 0 - 0 C H2.~H. C H2·Cl
CH3
1 Na. 0 H
o
/" -fi- T -fi / "-
CH3 0
C H2 C H.C H 2.0~ I ~O.C H2. CH C H2
CH3
Reaction 12
Chain extension and cross-linking mechanisms involve attack on the epoxy

groups. Higher homologues (n > 1) are favoured by more alkaline conditions
and reduced excess of epichlorhydrin (Reaction 13);
Reaction 13
These reactions favour the formation of hydroxyl group along the chain,
broadening the choice of curing agent to produce cross-linking. In addition,
many analogous resins have been derived, typically from epichlorhydrin and a
variety of compounds having active hydrogen atoms - usually hydroxyl
compounds. Epoxide resins are characterized by viscosity (for liquid resins,
n = 1-3), epoxide equivalent, hydroxyl equivalent, molecular weight and
distribution, melting point of solid resin and heat distortion temperature ofthe
cured resin.
Cross-linking can proceed through a number of mechanisms. Tertiary
amines and boron fluoride complexes catalyse homopolymerization
(Reaction 14);
-
!
- el:".
Reaction 14
Primary and secondary amines are employed (as Reaction 15);
Reaction 15
Acid and acid anhydride hardeners are less volatile and so safer to use. They
give lower exotherms, but will react both with the epoxy and hydroxyl groups
in the oligomers (Reaction 16);
o
II
0
II
HOC.R.COH +
,
,r,
{
OH 0 0 :,OH/
I II 11 1- --
/'V C H. C H 2. 0 C. R. cO. C H 2· C H"'-'
Reaction 16 (acids can also react with hydroxyls)
The availability of hydroxyl groups in the epoxide molecule permits

reaction with isocyanates and PF oligomers, particularly in the manufacture
of surface coatings. Many of the reactions shown above are slow, needing high
temperatures to produce complete cure. Applications include mouldings
where good properties and tolerances are essential, for example the encapsul-
ation of electronic components; however, epoxides are meeting some
competition from cheaper polyurethane resins. Metal shaping moulds,
prototype low-pressure moulds for epoxides, polyurethanes, thermoforming
moulds, etc. are often based on reinforced epoxide resins with high loadings of
cheap filler to maximize life and reduce cost. Resin-based tools are consider-
ably cheaper to fabricate than steel and aluminium alloys, lending themselves
to be built-up or cut away, if small changes are required. The largest uses of
epoxides are in surface coatings and adhesives, particularly for metal-metal
and metal-plastics bonding_ Floor coatings, aggregate-filled road surfacing
and marine coatings (for example for oil rigs), with heavy wear resistance, are
particularly important uses of epoxides as coatings. Epoxide resins are used in
fibre composites where polyester or silicone resin composites will not suffice,
for example where environmental problems, fatigue life and creep resistance
are critical. Examples include carbon-fibre-reinforced leaf-springs for public
transport. For ease of handling, a thixotropic resin (pre-mixed with heat-
activated curing agent) is used to pre-impregnate glass cloth, which can be cut
and shaped in a heated mould, similar to SMC. The pre-pregs eliminate the
handling problems of liquid resins, especially for those moulders who need
only small quantities of material, such as in passenger aircraft flooring.
References
1. Brydson, I.A., Plastics Materials, IliITe [Butterworth], London (1982).
11 Polyurethane plastics
11.1 Introduction
The polyurethanes (PU) offer the widest choice of properties of any group of
plastics materials, and the opportunity to incorporate specific chemical
structures into a PU chain allows the polymer chemist to tailor many specific
properties into the polymer. Therefore thermoplastic, thermoset resinous and
elastomeric PUs are available, many of them in cellular forms. Specific PU
properties include abrasion resistance and general ease of processing.
The choice of properties stems from the vast number of monomeric and
oligomeric ingredients that can be reacted together to produce polymers
containing the urethane group in their molecular structure. The urethane
linkage results from the reaction between isocyanate and hydroxyl-containing
compounds; catalysts and/or heat accelerate the reaction:
rvR'.N=C=O + rvR·.O-H -
rv R'- N - C - 0 -R",,-,
I II
H 0
The reactivity of many isocyanates is exploited by promoting side reactions,
either within the polymer chain or at chain ends, with reactive additives such
as chain extenders or cross-linking agents. The ease with which many
monomeric ingredients are converted into polymer during the shaping
operation permits relatively simple and cheap processes to be employed, often
with low expenditure of energy.
PU s find use virtually in any field of application: products can be shaped by
traditional thermoplastic processes, and by coating or calendering on to
substrates. However, the major manufacturing techniques involve dual
component processing of the liquid 'monomeric' ingredients. Products made by
such methods include slabstock and moulded foams; self-skinned foamed
elastomers and resins, and non-foamed mouldings made by reaction injection
moulding; surface coatings, sealants, encapsulants and adhesives. Foamed
PUs are used in a wide range of products from cushioning materials for
furniture and automotive seating, to thermal insulation, structural stiffening
for building panels or refrigerators. High-quality mouldings include automo-
POLYURETHANE PLASTICS 175
tive panels (glass-fibre reinforced), head restraints, steering wheels, car trim
and covers for electronic equipment. References listed at the end of this chapter
give comprehensive details of the properties of PU materials.
11.2 Molecular structure-property relationships

A polyisocyanate and a polyol (a polyhydroxyl material) are the basic
ingredients that react to form a polyurethane: polyols with functionalities from
2 to 6 are commonly used. Low-molecular-weight polyols (functionality 2 and
higher) or chain-extending diols, will tend to impart rigidity into a Pu.
High-molecular-weight polyols, (functionality 3 or less) will tend to give
softer, low-modulus PUs. It follows that the ratio of polyol to isocyanate
(the stoichiometry that will allow a reaction to form a full urethane polymer)
is high for high-molecular-weight polyols and low for low-molecular-weight
polyols. In addition, the amount of isocyanate reacted with polyol can be
varied around the theoretical stoichiometry, that is, by changing the iso-
cyanate index. A low isocyanate index may tend to encourage plasticization
of the PU because of the presence of excess polyol, and a high isocyanate
index will promote stiffening through cross-linking side reactions (see section
11.2.1). However, to produce thermoplastic PUs, reactants with a func-
tionality of 2 mixed at precise stoichiometric proportions must be used.
Cellular PUs are relatively cheap to manufacture, and dominate the market-
place, even although the cost of raw materials may be at least twice that for
foamed commodity thermoplastics.
11.2.1 Typical reactions

Isocyanate under suitable conditions will readily react with active hydrogen-
containing compounds.
rvR'. N=C=O +
(i) Isocyanate/water
rv R. N=C= 0 + rv R. N H 2 ~
I
o
II H
rv R-N-C -N -R--v
I I
H H
(ii) Isocyanate/amine (poly urea formation)

-
II
H
I
H
I "I
rvR'. N=C=O + rvR-N-C-N-Rrv
~
o H
" II I '.
rvR-N-C-N-Rrv
I
C
-::-.......... ,
o N -R""-'
I
H
(iii) Isocyanate/urea (poly biuret formation)
oII
rv R'. N=C=O +
II
rvR - N -C - 0 -R""-'
H
I
II,
-
(
oII III
rvR-N-C-O-R""-'
I
' iC,
o N-R'rov-
H
(iv) Isocyanate/urethane (polyallophanate formation)
o
II
O=C=N-R, /C, /R-N=C=O
N
I
N
I
3 O=C=N -R - N=C=O - C'N/ C ~
~
01 0
R 'N=C=O
(v) Isocyanate/isocyanate (e.g. isocyanurate formation)
The side reactions (iii-v) lead to cross-linking, and will readily occur with the
polyoljaromatic isocyanate reactants at ambient conditions, if both the
appropriate catalyst and slight excess isocyanate are used, even though
the isocyanate may be di-functional. Urethane cross-links also readily occur
with polyols or isocyanates of functionality 3 or higher.
11.2.2 Monomeric components
(i) Polyols. Typically these are oligomers derived from several classes of
hydroxyl-containing material. Polyether polyols are typically made by
reacting ethylene or propylene oxides with water in the presence of alkaline
catalysts; these are made in the molecular weight range of 600 to 6000.
II
o
/'-...
H2 C-C.H.R -- ~
H OtC H2. C.H-Or H
n.
(R= H,CH3)
Polyethers are used in the manufacture of flexible foams, giving good
resilience and hydrolytic stability, and are the basis of many PU.RIM systems,
although they have limited thermal stability (to a maximum of 70°C).
Polyester polyols are made by conventional polyester processes (for example
adipic acid reacted with butane-I, 4-diol), although the diol is used in slight
excess to ensure that the resulting oligomer has hydroxyl-tipped chain ends:
again, the molecular weight range is between 600 and 6000. Speciality
polyesters are made from the reaction of e-caprolactone with low-molecular-
weight diols (e.g. ethylene glycol) or triols (e.g. glycerol).
Polyester polyols impart better mechanical properties and thermal stability
to the PU, but have poorer hydrolytic resistance than the polyethers.
Polyesters are used in large tonnages for shoe soling, some flexible foams, and
many elastomer formulations. Polyols with functionality greater than two are
produced from a wide number of sources, such as propylene oxide reacted with
glycerol or sugars (for polyols offunctionality 3 and 6, respectively), and other
naturally-occurring materials. Sugar-based polyols are used to give high
rigidity in low-density structural foams, although higher-molecular-weight
polyether polyols may be included in a polyol blend to reduce brittleness. The
ease with which many other compounds can be further hydroxylated broadens
the variety of starting monomers; polybutadiene, for example, is polyhydro-
xylated to permit isocyanate vulcanization. Polyethers are largely low-
viscosity liquids at 15°C, permitting easy processing; polyesters tend to be
either viscous liquids or waxy solids and need to be heated to effect processing.
Polyols are characterized by hydroxyl value, water content and molecular
weight.
(ii) Isocyanates. The choice of polyisocyanates is more limited. Of the
aromatic isocyanates, toluene diisocyanate (TO I), and 4,4' -diphenylmethane
diisocyanate (MOl) are commonly used.
Y
NoC
H3 N=C=O
lDl
N=C=O
O=C=N -0 ~ -oN:C=O MDI
TDI is made by the nitration of toluene, to give dinitro derivatives, which are
hydrogenated to the diamines and these in turn are phosgenated to the
diisocyanates. Typically, a 80:20 mixture of the 2,4 and 2, 6 isomers of various
purities is employed; they are low-viscosity liquids down to O°e. MDI is made
by the phosgenation of diamino-diphenylmethane, itself formed by the
condensation of aniline and formaldehyde. Pure MDI is an unstable solid
(melting point 42°C), readily forming dimers and trimers. 'Polymeric' or
'crude' MDls are fractions distilled from the reaction products, having
functionalities of 2 to 3. The so-called commercial 'pure' MDIs are eutectic
mixtures of pure MDI and products derived from the reaction of excess pure
MDI with diol (e.g. butane-I, 4-diol); these have a melting point of 10-20°C
and a functionality of 2. Aromatic isocyanates are relatively expensive (£ 1000
to £1500 per tonne). Isocyanates are characterized by isocyanate content and
chloride content.
Unfortunately, the aromatic isocyanate component in a PU chain may
contribute to poor oxidative resistance, particularly under UV-radiation.
Employing mixtures of stabilizers has limited success in eliminating embrittle-
ment or yellowing. Alicyclic and aliphatic isocyanates give good resistance to
UV, (e.g. isophorone diisocyanate), finding use in products for exterior
applications (e.g. surface coatings) but are more than five times as expensive
and tend to be less reactive than the aromatic types.
The high reactivity of isocyanates together with their volatility gives rise to
health and safety problems. A solution to volatility is to produce isocyanate-
tipped PU pre-polymers, by reacting excess isocyanate with polyol under
controlled conditions: the oligomer can react with active hydrogen species
some time later. This will also permit controlled development of the structure
of a PU, especially when using mixtures of polyols.
(iii) Other additives. Chain extenders are normally low-molecular-weight

diols which impart limited rigidity into the PU chain. Di- and triethylene
glycols, mono- and di-propylene glycols and butane-1,4-diol are most
commonly used. Cross-linking agents include high functional polyols, and
diamines (functionality 4). Polyurea-polyurethane copolymers with
superior properties are produced from 3,3' -dichloro-4, 4'-
diaminodiphenylmethane (MOCA) although it is a suspected carcinogen.
Polyamines derived from propylene oxide are used in the high-speed
polyurea/polyurethane reaction injection moulding process in the manufac-
ture of automotive panels (see section 11.3.3).
Most PU processes involve the simultaneous making and shaping of the
polymer at room temperature and employ catalysts. The urethane reaction is
catalysed by organic metal compounds, typically tin salts and tertiary amines.
The water/isocyanate reaction is catalysed by amines; again the tertiary
amines are preferred over primary or secondary amines, since they have little
odour and do not react with isocyanate. Many side reactions are promoted by
heat (e.g. from reaction exotherm) and by catalysts, for instance in the
formation of the allophanate cross-link. Residual catalyst in PU products will
accelerate degradation in adverse conditions.
The water-isocyanate reaction forming carbon dioxide is commonly used
to form open-cell flexible foams. Trichlorofluoromethane (TCFM) is a
physical blowing agent relying on heat from the urethane reaction exotherm to
boil: this is used to form rigid closed-cell foams and most self-skinned
moulded products. There is considerable concern over the effect of flu-
orocarbons on the Earth's ozone layer, and suitable replacements are actively
being sought.
Surfactants acting as nucleating agents are used to control foam cell size and
distribution; materials including modified silicone oils are dissolved into the
polyol ingredient stream. Rigid foamed PUs which have to be painted
following moulding will include dissolved air-in-polyol as a nucleating agent,
to ensure subsequent paint adhesion. Pigments are used to give solid colour to
products, although surface coatings for the moulded product are now used,
because MDIs are dark and contribute to poor UV stability of the PUs. Fillers
are used in reaction injection moulded (RIM) products reinforced with
glass fibre, used to reduce high coefficient of thermal expansion and creep
(Table 11.1). The glass is in the form of short hammer-milled or chopped-
strand fibre (O.2-3.0mm in length), long enough to give reinforcement (aspect
ratio greater than 10), but short enough to be pumped through dispensing
Table 11.1 The effect of glass fibre on the properties of high-modulus polyurethane elastomer'
Glass content (%wt)

Property Orientation 2 0 10 20 30
Density (kg m - 3) 1100 1150 1200 1300

Flexural modulus Par 350 600 1000 1500
@ 23°C (MPa) RA 400 550 700
Coeff. of thermal Par 180 70 40 25
expansion (x 1O- 6 tC) RA 165 140 130
Heat sag, 1 h at 160°C Par 15 8 5 3
(mm) RA 11 10 8
Elongation at break Par 320 250 180 5
(%) RA 250 200 140
Notes:
1. Based on information for glass-reinforced Bayflex™ GR 110/50 (using 0.2 mm length hammer-
milled glass fibre); Bayer leaflet PU52113e. For further details, see Seel, K. and Klier, L.,
Reinforced polyurethanes for car body parts, KunststofJe 71 (1981) 9, 577-584.
2. Orientation based on the flow direction from injection point of the mould: Par, parallel to flow;
RA, at right-angles to flow.
machinery without attrition of fibres or abrasive wear of the equipment. The

glass fibre used in reinforced flexible PUs does not have to be surface-treated,
since some fibre slippage is desirable in the flexible PU matrix.
11.3. Properties and applications of polyurethanes
11.3.1 Flexible polyurethane foams

The major use of PUs is in flexible foams, for upholstery, mattresses and
vehicle seat cushioning. Semi-flexible grades are used as in-fill materials, for
instance as an energy-absorbing composite backing plasticized PVC skins on
car crashpads (part of the dashboard).
Cushion foams are made by both slabstock and moulding techniques. In
large-volume slabstock production, the one-shot process is used; polyol,
isocyanate, catalysts, blowing agents (such as water) and surfactants are
metered separately and pumped to a mechanical mix-head, where the
ingredients are mixed rapidly together and poured either into a moving
'trough' (Figure 11.1), or a large box mould, making slabstock loaves or buns
respectively. The ingredients react and expand to fill the trough or box; the
foam will be fully expanded and the surface of the foam dry to the touch in less
than 10 minutes, although complete cure will take longer. The freshly-made
blocks are stored in warm rooms to speed complete cure and allow volatiles to
evaporate. The blocks are cut by bandsaw to the required shapes; waste PU
foam can be reconstituted by gluing foam crumble together, and this can be
used as a stiffinfill for seating. The cut foam can then be covered with fabric to
make seating, or mattresses. The inherently poor fire retardancy ofthe PU can
be improved by incorporating halogenated phosphorus compounds,
or by covering with fire-retardant fabric or interliners.
Moulded cushions tend to have slightly better fire retardancy and better
resilience properties than slab-stock products. Hot-cure and, more recently,
cold-cure moulding techniques have allowed better control of the side
reactions (such as formation of isocyanurate and allophanate cross-links).
One-shot processing with low-pressure dual-component dispensing equip-
MIX-HEAD
EXPANDED pu.
PAPER
Figure 11.1 Diagram of continuous foam slab stock production

ment is used, the polyol being pre-blended with all the other ingredients except
the isocyanate. For better control ofthe reaction and residual by-products like
unreacted isocyanate, isocyanate-tipped prepolymers are used, in the so-called
two-shot process; the prepolymer is reacted with water and polyol in the
foaming reaction. The mixed ingredients are poured from the mix-head into a
heated mould coated with release agent, the lid of which is closed as the
reaction starts. Heating will ensure, and accelerate, important side-reactions
(Figure 11.2). Demould is within ten minutes. Changing the stoichiometry of
the ingredients by closed-loop control of pumps allows the manufacture of
products such as up-market car seats with foamed sections of different moduli
to be made in a single moulding operation. The density of the open-cell PU
foams ranges from 20~100kgm-3. Until the late 1970s, TDI was the
Figure 11.2 Production of hot cure moulded flexible PU foam

dominant isocyanate used, but as a result of increasing concern over the health
risks, MDI and TDI/MDI blends are now more popular.
11.3.2 Rigid polyurethane and polyisocyanurate foams

Rigid PU resins can be readily foamed to low densities, giving excellent
insulation and imparting stiffness to many products such as panel walls and
refrigerators. Again, the problem of poor fire resistance has led to the use of
halogenated phosphorus compounds as fire-retardants and also to the
development of PU/polyisocyanurate foams. Slabstock techniques are used,
where the cut closed-cell foam can later be adhesively laminated with any of a
number of facing materials such as plasterboard, paper, or metal foils. A
popular manufacturing technique involves pouring the mixed liquid ingre-
dients directly on to a contino us band of facing material, allowing partial
expansion of the foam before applying an upper facing; full expansion and cure
of the PU will then be accelerated by heat (Figure 11.3). Rigid foam can be
injected easily into any cavity formed in a product: between the two skins of a
domestic refrigerator, or into the void formed by the two sheet-steel skins of
factory door and wall panels. Although the mixed liquid ingredients are
mobile, the rapid reaction and increase in viscosity mean that the placement of
the material has to be facilitated by optimum mould orientation (in the case of
the refrigerator), or by placing an extended nozzle of the mixhead into the
cavity, then gradually withdrawing it as local filling is achieved (Figure 11.4).
The ease with which PU ingredients can be processed permits their
application away from the controlled factory environment, using in-situ
dispense equipment, such as on a building site for cavity wall-fill or storage
tank insulation. A diesel generator runs high-pressure pumps and heaters
which are used to dispense materials through an impingement mix-head;
ingredients can be pumped a distance of up to 100 m. Mix-heads can be fitted
FACING MA TER IAL

(UNWIND)
EXPANDED FOAM
FACING MATER IAL

(UNWIND)
Figure 11.3 Diagram of the continuous production of rigid foam-filled panels
NOZZLE
EXPAND I NG FOAM EXTENSION
SEALED
END
MIX-HEAD
GR"DU"LLY
REMOVED AS
FILLING I S
COMPLETED
F"C I NG
PANELS
Figure 11.4 Diagram of batch production of rigid foam-filled panels
with nozzles for either spraying (to cover a large surface area) or pouring (for
cavity fill). Ingredients are pre-heated to ease pumping, overcome low ambient
temperatures and give very high reaction rates (less than 10 seconds),
preventing slump on vertical walls. Damp conditions have to be avoided.
Thick elastomeric coatings or sheet are used to protect the cured PU foam
from direct sunlight.
Moulded high-density rigid foamed PU products (200-750 kg m - 3), are
finding increasing use, for example in energy-absorbing blocks for car
Figure 11.5 A chest made up of decorative 'antique' panels based on barrier release coated rigid
PU foam. By permission of Oakleaf Reproductions
bumpers, decorative panelling, or soles for clogs. Because of the initial low
viscosity and wetting properties ofthe mixed ingredients, a PU will accurately
reproduce the detail of a mould surface. This is particularly exploited in
flexible mould techniques. Usually a wooden carving (the master) is made, and
a silicone rubber pull cast from it, which is used as the liner of an epoxide
mould. To increase the life of the silicone mould (up to 100 mouldings), an in-
mould barrier release surface coating has to be used. The coating also means
that a component out of the mould will process in the same way as a primer-
coated piece of timber: it can be finished using traditional wood-staining and
lacquering techniques. The finished product has all the appearance of the
original master. Use offlexible silicone or PU elastomeric liners permits a high
degree of three-dimensional relief in the product. Kitchen cabinet doors,
decorative panels and beams, and ornate picture frames are made by this
technique (Figure 11.5).
11.3.3 Reaction injection moulded polyurethane products

The advent of high-pressure metering and impingement mixing of PU ingre-
dients through self-cleaning mix-heads has provided a process method which
allows PUs to compete with high-quality thermoplastic injection moulding,
for example for large automotive panels and electronic component housings.
Although some products can be made using high-pressure open-pour
moulding techniques, reaction injection moulding (RIM) involves closed
moulding processing of flexible or rigid self-skinned foams, or high-modulus
elastomeric products. Modified RIM equipment is used to process reinforcing
fibre-filled PU/polyurea systems (RRIM).
RIM cycle times range from 45 seconds to 10 minutes, although the
application and drying time of release agent may take up to 60 seconds. In the
mass production of smaller mouldings, it is not prohibitively expensive to
employ a number of identical moulding tools (based on epoxide liners in
aluminium for example) loaded on to a carousel moulding unit. The carousel
can hold up to 50 moulds; these progress past a lightweight RIM mix-head,
which can be readily attached to and detached from each mould for filling.
This allows the manufacturer a high output, although unit cycle time may be
about 10 minutes. In PU-RIM systems having longer mould cycles, the
high-pressure dispense unit can be used to feed several mix-heads bolted
on to separate moulds in their own clamping presses, via ring-main/manifold
units.
Mixed ingredients leave the mix-head nozzle at velocities up to 2 m s - 1, and
gating into the mould cavity must be carefully designed to prevent turbulent
flow with the associated problem of air entrapment. As PU systems may react
within a few seconds, filling of larger mould cavities becomes particularly
critical to prevent underfilling or weld lines, which will give structural
weakness in the product. Liquid PU ingredients will readily flow into the
mould cavity, but the low pressure involved means that mould orientation, the
filling point and split-line locations must be chosen with care, to ensure that air
is fully expelled by the moving front of liquid ingredients entering the cavity.
Possible moulding faults include underfilling, air-traps and density gradients
in cellular products (in vertical or inclined sections).
PU-RIM systems are normally microcellular, high-modulus elastomers,
based on polyether polyols - 'pure' MDI systems, although better high-
temperature performance is achieved using polyamine - polyether polyol
systems. Foam formation and self-skinning is promoted by trichlorofluoro-
methane (TCFM) or methylene chloride blowing agents. The ingredients
injected into the mould cavity react and exotherm, boiling the TCFM and
starting the foam formation. A little of the TCFM will escape into the air space
of the mould cavity, rapidly condensing on the walls of the mould under
pressure. The combination of the foam collapsing as it expands into the
mould walls, due to the surfactant action of the liquid TCFM and overpacking
of the foam in the mould cavity, produces a high-density skin on the surface of
the moulding. Automotive steering wheels and head restraints are produced in
this way.
Both products are made in a similar manner. Release agent is applied to the
clean mould surface and allowed to dry. To overcome the problems of poor
UV stability and to reduce production costs, a surface coating is sprayed on to
the mould surface and allowed to dry. Mould temperature is 40-90°C to speed
Figure 11.6 Production of a car steering wheel moulding using modified RIM equipment. By
permission of Sheller Clifford
paint drying and, subsequently, the foam reaction (Figure 11.6). A metal
insert, intended to give rigidity to the product, is placed in the mould, which is
then closed. A high-pressure mixing-head is clamped to the inlet port of the
mould and a shot of mixed ingredients fired into the cavity. The head is swung
away and the expanding foam is allowed to just spill out of the mould before its
inlet is plugged. The mould is heated to speed the reaction, either by internal
water channelling or by transferring it to an oven, in the case of a number of
small moulds on a carousel line. The product can be demoulded in a few
minutes, and deflashing removes a thin line of oversprayed paint. The in-mould
PU paint appears to give near-perfect adhesion with the substrate. Shoe-soles
are made from polyester - 'pure' MDI systems using similar techniques: again,
dual-density foams can be made in a one-step process by an index change of
the reactants.
(i) Self-skinned semi-flexible polyurethanes. These give a soft and comfortable

feel, with excellent abrasion and stain resistance. The foam will act as a shock
absorber, for instance if a car driver is thrown against a steering wheel or head
restraint. The poor resistance to UV exposure and the limited range of colours
of PU has led to the successful use of barrier coats based on non-aromatic
isocyanate-based-PU surface coatings. The accuracy with which PU repro-
duces the detail of the mould surface allows the stylist to use subtle textures.
PU currently dominates the steering-wheel market (approximately 80% in
Europe); polypropylene has the only other significant share. Although subject
to fashion changes, the PU head-restraints are used in many down-market
vehicles. Shot weights of ingredients will be under 750 g, with less than 5%
wastage (from runners, etc.). Integral-skin components made in one produc-
tion step have replaced components fabricated from stitched fabric or
rotational moulded plasticized PVC, reinforced with a steel frame and filled
with PU foam in a second process operation (Figure 11.7).
(ii) Self-skinned rigid polyurethanes. These are used for office and kitchen
furniture and housings for electronic components such as television cabinets in
the range 4-15 kg moulded weight, and are made by using dedicated mix-
head/mould combinations. Many ofthese foamed products have to be surface-
coated. From the mould, the product is allowed to post-cure at room
temperature before solvent-degreasing to remove release agent from its
surface. Degreasing is aided by sanding using emery cloth, which will also
eliminate the flash-line scar while creating fine scratches in the surface to
enhance paint adhesion. Any small holes in the moulding'S surface have to be
filled at this stage using unsaturated polyester or cellulosic putty. The
moulding is normally primer-coated, then lightly resanded before a topcoat
paint is spray-applied. Generally the post-moulding operations are the time-
consuming and labour-intensive steps in the production; because of this, rigid
Figure 11.7 Range of in-mould coated, semi-rigid, self-skinned PU foam mouldings. By

permission of Marley Foam, Sheller Clifford and Bridgtown Industries
Figure 11.8 Preparation of a chair moulding based on rigid PU-RIM for post-mould painting
integral-skinned PUs face severe competition from self-coloured foamed

thermoplastics like ABS and polycarbonate. Compared with non-foamed
plastics such as modified PP, foamed PU in particular offers the designer the
opportunity to use thicker sections (10-20mm) giving 'body' and elegance to
the shape of a piece of furniture (Figure 11.8).
(iii) Solid and micro-cellular elastomeric polyurethane RIM products. These

are used largely in the production of exterior automotive components: wheel
arches, bumpers, panels, and many add-on units employed to enhance the
appearance and cost of up-market versions of cars. Legislation to improve fuel
consumption by weight reduction and to reduce collision impact damage has
led to the acceptance of plastics as car bumpers, replacing chromed steel. In the
USA, the original 5 mph requirements for damage control resulted in the use of
high-modulus PU elastomers, which would buckle under the impact load then
fully recover, even at speeds up to 10 mph. Vehicle stylists realized that plastic
bumpers could be designed to provide large complex shapes with a greater
number of functions than the traditional metal components, for example
complete (soft) front and rear ends for cars. In Europe, the 5 kph (3 mph)
requirements subsequently introduced by the EEC opened the door to
engineering thermoplastics in preference to PUs (exceptions included the
Jaguar XJS and MGB GT bumpers).
Some automotive companies such as British Leyland (now Austin Rover)
prefer complete on-line painting for exterior panels and bumper assemblies,
meaning that any plastics component will have to withstand the same paint
stoving conditions (150 a C or higher, for up to 30 minute) that sheet steel under-
goes. Under these regimes, PUs will suffer heat distortion, while modified poly-
carbonates will become stress-crazed by the paint solvent. The alternative
is to pigment and stabilize the moulding in a neutral colour: black for PUs,
light grey or brown for polycarbonate-polyester as used on the European
Ford Sierra. Few plastics can take such stoving conditions; these include
modified poly(butylene terephthalate), unsaturated polyester SMC, and glass-
reinforced polyurethane/polyurea and polyureas. Short-strand glass fibre (up
to 20% loading by weight) in the PU/polyurea system increases modulus,
reduces coefficient of thermal expansion (when installed with metal panels,
thermal expansion and contraction is less likely to show either as distortion
around the fixing points or as large gaps between the panels, respectively), and
reduces heat sag and creep in service (Table 11.1). In the USA, there is
relatively large volume use of reinforced PU-polyurea, as in the Pontiac
Fiero's body panels, but a radical change in vehicle assembly methods has had
to be adopted (Figure 11.9). In Europe these materials will be found only on
low-volume-number vehicles, e.g. Porsche (soft rear ends), Reliant Scimitar
SSI (body panels), Rolls Royce Silver Spirit (front spoiler), although it may be
speculated that in mass vehicle production there will be wider acceptance as
faster PU or poly urea systems become available.
Figure 11.9 Pontiac Fiero made up of exterior plastics components fixed on to a load-bearing
steel skeleton, including PU-RIM side panels, glass reinforced PU-RIM door panels and polyester
SMC bonnet and roof panels. By permission of Bayer (UK)/UT
11.3.4 Elastomeric and resinous thermosetting polyurethanes

Good abrasion and chemical resistance in many environments, combined with
ease of application at room temperature, has led to wide use of PU elastomers.
Products range from covers for printing-press rollers, abrasion-resistant lining
materials, to low-speed tyre filling and vehicle floor mats. Synthesis can be
either by one-shot (polyol reacted with isocyanate) or two-shot process (a
prepolymer is first made, normally with isocyanate-tipping, which can later be
reacted with a curing agent, e.g. diols as chain extenders or polyamines or
triols as cross-linking agents), or with atmospheric moisture if applied as a thin
film. Diamine-cured prepolymers give excellent products; an example is the
sound-proofing covers for pneumatic drills used in mining and quarrying
where good environmental and abrasion resistance is a prerequisite.
Polyether~MDI systems can be sprayed in factory or in-situ applications, to
provide abrasion- and corrosion-resistant coatings (in quarry conveyor
buckets, hovercraft propeller blades, water-inlet ducts for power stations and
in many civil constructions such as oil rigs; in these applications the PU may
need to be applied in 'films' up to 50 mm thick - Figure 11.10). Energy-
absorbing PU elastomers (e.g. Sorbathane™) are used to line motor-cycle
crash-helmets; these are based on polyether polyol~MDI systems where either
plasticizers or excess polyol (low isocyanate index) are used.
Figure 11.10 In-situ spray application of a 100% solids PU elastomer to the interior of a pipe. By
permission of Lithgow Saekaphen Ltd
The resinous or rigid PU systems lend themselves to room-temperature

mixing and dispensing, often by hand. High loadings of selected fillers are used
as cheapeners, to improve electrical properties and give dimensional stability
in mouldings-hence their use in the encapsulation of electronic components
(such as in starters for street lighting), as insulators for high-tension power
lines, on-site applied sealants for cable splice boxes, and for self-levelling
flooring systems. PUs compete with epoxide resins in this field.
11.3.5 Thermoplastic polyurethanes

In comparison to other types of PUs, thermoplastic polyurethanes (TPPU) are
oflimited availability and end-use, although they were amongst the first PUs
to be developed in the early 1940s, as competition to polyamide fibres. Again
they are exploited for their abrasion resistance, over a range of hardnesses
from 50 Shore A to 80 Shore D. Basic thermoplastic injection-moulding and
extrusion equip'ment can be used to process TPPU, although the polymer
granules should be dried before melt processing, to prevent degradation. Uses
include the exotic-TPPU replaces goose feathers as flights for archery arrows,
because the snap-back characteristics are similar. It has also been used for
combined sleeping policeman/cable protectors for geophone cables used in
built-up areas. TPPUs can be blended into plasticized PVC and elastomer
formulations, to improve stiffness and modulus without loss of low-
temperature properties, for instance in shoe soles. Recently a range of alicylic
isocyanate/caprolactone polyester TPPUs has been developed for UV-
resistant, water-white safety materials such as face shields. These have superior
abrasion resistance to polycarbonate, more commonly found in this
application.
11.3.6 Polyurethanes as surface coatings, adhesives and sealants

A wide range of starting materials can be used to form PU with virtually any
selected properties. This is nowhere better exploited than in the surface
coatings and adhesives industries. The chemistry and surface-tension pro-
perties of PUs allow wetting and excellent physical interfacial bonding with a
wide range of substrate materials, and this is enhanced either by allowing PU
Figure 11.11 A two-pack, low stove PU vehicle paint system, used as an exterior finish for the
Panther Kallista
reactants to react directly on the substrate's surface, where isocyanate will tend
to form strong covalent bonds, or by dispersing reactants in suitable solvent
carriers.
The abrasion characteristics of PUs are again exploited in surface coatings,
along with resistance to chemicals, ease of application, and low-temperature
drying and curing. Uses include urethane alkyds for house paint: one- and
two-pack paint systems (as motor vehicle finishing and refinishing paints,
Figure 11.11), varnishes (e.g. for marine timber and electrical wire lacquers) or
inks. Isocyanate-tipped PU prepolymer two-pack systems are popular in
industrial applications, curing by reaction either with atmospheric moisture
or with suitable curing agents. UV-curable PU/acrylics are used as paper
finishes and cabinet door lacquers.
Adhesives can be based on either reactive or fully reacted PU systems. Large
quantities of PU are used in contact adhesives in the construction industry.
PU sealants normally rely on moisture curing, for instance sealants used for
wooden frame constructions in domestic housing.
Further reading
Hepburn, c., Polyurethane Elastomers, Elsevier-Applied Science, Amsterdam (1982).
Woods, G., Flexible Polyurethane Foams, Elsevier-Applied Science, Amsterdam (1982).
Becker, W., Reaction Injection Moulding, Van Nostrand Reinhold, New York (1979).
-, Polyurethanes, Bayer pub!. (PU50025e), Bayer AG, Frankfurt (1979).
Woods, G., The leI Polyurethanes Book, Wiley, Chichester (1987).
Index
abrasion 101, 139, 192 lamp covers 63

acetal plastics 117 radiator reservoir tanks 80, 81
copolymer 117 seating 180 - 1
glass fibre-reinforced 123 steering wheels 185
. homopolymer 117 screen wiper gear 118 - 20
acrylonitrile - butadene - styrene (ABS)
plastics 54 baths, PMMA 63
blends with polycarbonate 69 battery cases 77, 78
blends with poly(vinyl chloride) 133 benzoyl peroxide 163
acrylonitrile - styrene copolymer 52 biaxial orientation 112
additives 7, 93 biuret 176
adhesives 160, 173, 191 blends, polymer 49, 56, 74, 116, 117.
hot melt 116 133
ageing 6 blowing agents 85, 129, 156, 179
alkyd resins 148 blow moulding 13, 34, 41, 89, 94
allophanate 176 Injection IS, 34, 94
amide plastics bottles, stretch blown 15
aromatic 111 butene 87, 100
copolymer 104 butylene terephthalate 111
glass fibre-reinforced 106, 108 glass fibre-reinforced 115
mineral-filled 107 blends of with PC 69
PA 66 103 t-butyl perbenzoate 163
PA 6 103
PA 6.10 103 cable avoidance tool 40
PA 11 103 calendering 8, 12
PA 12 103 car components see automotive
PA 4.6 103 components
PA MXD.6 103 carbonates 60, 66, 140
rubber-modified 108 blends of with ABS 69
aminoplasts 148 blends of with PBTP 69
amorphous plastics, shrinkage of 40 embrittlement of 67
anisotropy 107 transparency of 69
anti-blocking additive 7 toughness of 67, 69
anti-oxidant 7, 73 cellulose plastics: 60, 64
UV-siable 73 acetate 65
anti-plasticization 129 acetobutyrate 65
automotive components esters 64
body panels 167, 169, 188 ethers 64, 66
fascias (crash pads) 58, 133, 180 nitrate 65
fenders (bumpers) 82, 116 propionate 65
fuel tanks 89, 90 regenerated 64
head restraints 185 chain extenders 178
heater boxes 83 chemical properties 6
indicator switches 122, 153 - 5 chlorinated dicarboxylic acid 164
193
194 INDEX
chlorinated polyethylene blend with low-pressure 19

PVC 133 spray 182
chopped strand mat 165 dust explosions 72
coating see surface coating
cobalt naphthenate 163 economics, processing 40
cobalt octoate 163 elasticity, linear 23
colour 5 electrical properties 5, 93, 106
composites 7 electric drill casing 107
long-fibre 39 electric strength 5
short-fibre 38 electroplating 86
compression moulding 16, 151 engineering design 23
conductivity, thermal 4 enthalpy (heat content) 4
containers large-capacity 89 environmental stress cracking 6, 59, 93
cooling, internal (for blow moulding) 89 epoxide resins 145, 170
copolymerization 49, 74 cross-linking reactions in 172
costs of plastics esters
materials 24 glass fibre-reinforced poly- 108, 164
production 41,42,43,45 in plasticizers 128
crack growth rate 33 as prepolymers for PUs 177
crack propagation 91 thermoplastic 111, 116, 117
crazing 62, 188 unsaturated poly- 148, 163
creep 23,25, 54, 57, 62, 75, 88, 89, 112, ethersulphone, poly- 141
114, 126, 136, 138, 139, 141, 142, glass fibre-reinforced 103
188 ethylene
critical oxygen index 65, 69 copolymers of 87, 100
cross-linked plastics 1, 6 linear low density 87, 94
shaping of 9, 16 low density 87, 92
cross-linking agents 178 as monomer 87
crystallinity 1, 6, 21 in polymer blends 87, 95 - 9
crystalline texture 21 very low density 87, 95
crystalline thermoplastics, shrinkage ethylene terephthalate, poly- 111
of 40 expansion, thermal 4
crystallization, effect of cooling rate explosions, dust 72
on 75 extractor fans 113
curing agent see cross-linking agent extrusion 10, 34, 89, 94
blow moulding 13, 94
degradation die 8
thermal 73
ultraviolet 178 fabrication 42, 43, 44
design 23, 35 failure
limitations on imposed by processing brittle 3
method 33 ductile 3
of gas pipe system 91 fans, extractor 113
design stress vs. temperature 126 fatigue 28, 30, 55, 105, 117
die extrusion 8, 11 fibres 7, 151
die sizing 11 fillers 7, 131, 151
differential scanning calorimetry (DSC) of film 13
PE blends 95, 96 fire properties
dinghy, 'Topper' sailing 86 of PF 157
dough moulding compound 167 - 70 of PP 86
dual component processing 17, 174 of PPS 145
dual component dispensing equipment of PPVC 129
high-pressure 19, 184 of PU 182
INOEX 195
flooring, vinyl sheet 132 of thermosets 16

floor tiles 133 injection blow moulding 15,41,44,94
fluorocarbon blowing agents 156, 179 integral hinge 76, 79
fluoroelastomers 135 intermittent loading (creep) 28, 29
as copolymers of VOF and TFE 140 ionomer resins 100
polychlorotrifluoroethylene 135 iron handle 146
poly(vinyl fluoride) 135, 140 isochronous stress vs. strain 25 - 7, 68,
poly(vinx!idene fluoride) 135, 138, 139 105
foams 1; 36, 37, 69, 84, 156, 160, 179;', isocyanate
180, 182 health hazard from 178
. sfrUctura1 31 reactions of 175, 177
syntactic 86 isocyanate index 175
formaldehyde sources isocyanurate formation 176
'hexa' 150 isometric stress vs. log time 25 - 7
paraform 150
fractional recovered strain 28 kettle 121 - 2
fracture mechanics 3, 30, 91
fracture toughness 32, 33 laboratory ware 10 1
friction of PTFE 136 laboratory ware 10 1
fuel tanks see automotive components laminates, PF 156
fumaric acid 164 latent heat of fusion 4
fusion, latent heat of 4 lifeboat in ORP 167
light, scattering of 5
gas barrier 103 linear elastic stress intensity factor 32
distribution of 89 - 91 linear ela~ticity 23
gaskets 82 load; intermittent (creep) 28, 29
glass fibre-reinforcement loss factor (electrical) 5
of thermoplastics 114 low-pressure dispensing 19
of thermosets 157, 165 - 8 low-pressure moulding 17
of urethanes 179 lubricant 7, 125
gloss 5
grill plastics components 115 maleic acid 164
growth rate of cracks 33 masterbath techniques 95
materials cost 24
hand lay-up 17,35,41-4, 167 mechanical properties 2
hardness of PMMA 61 (LOPE) effect of density on 93
haze, haziness 5 (LOPE) effect of MFI on 93
heat content (enthalpy) 4 medical use of PTFE 137
heat of fusion 4 melamine formaldehyde plastics 158,
hexamethylene tetramine 150 161
hexanone peroxide, cyclo- 163 melt flow index (MFI) 8, 73, 92
heater box (for cars and trucks) 83 melt properties 5
high-pressure dispensing 19, 184- 8 metallization 7
high-pressure moulding 16 methylethylketone peroxide 163
homogenization 8 methyl methacrylate, poly-
'Hovermower' cover 56 in blend with PVC 133
hydrolysis 112, 177 cast sheet 60
moulding powder and extrusion
imides, poly- III grades 61
impact strength 28 - 30, 54, 57, 62, 67, hardness of 61
73, 105, 125 light transfer in 62
injection moulding 11, 34, 41, 44, 45, transparency of 62
113, 151 4-methyl pentene, poly- 87, 101
196 INDEX
pthalic acids 164

mixing 8 pipes 89, 100, 106, 125-7
modulus plasticizers for PVC 128
flexural vs. temperature 69, 144 plastics, reinforced 36
tensile vs. temperature 112 plating 51
mould shrinkage 4, 48 plumber's tape 138
mould tools 8, 17,20, 173, 184 polymer, polymerization (see also
moulding faults 36, 184 individual monomers) I
moulding processes: polyols 176
compression 16, 151 powder blending 8
flexible mould 184 powder processing of PTFE 136
high-pressure 16 power factor (electrical) 5
injection ll, 44, 45, 94,113,151 prepolymers 9, 48, 149, 159, 161, 163,
injection blow 15, 34, 41 178
low-pressure 17 processing, economics of 40
reaction injection 35, 41, 46, 184-7 processing of thermoplastics 8, 10
rotational 13, 34, 41, 44, 45, 92, 94 product design 35
thermoset 16 production costs 41-43,45
transfer 17,151 properties, molecular
Natta see Ziegler - Natta catalyst 72 long-chain 2
novolak resins 149, 151 networks and 2
nucleating agents 5, 179 organic nature of polymers and 2
nylons see amide plastics properties, in-service
chemical 6
oligomers see prepolymers electrical 5, 93
optical properties 5 mechanical 2, 93
orientation melt 5
biaxial 112 optical 5
effect of on barrier properties 113 thermal 3
effect of on tensile strength 29 propylene plastics 51, 72
fibre reinforcement and 84, 106, 165, l3-crystalline form of 76, 77
179 blends of with rubbers 74, 82
toughness and 49 composites and 80, 82, 83
oxide catalyst for ethylene controlled rheology of 73
polymerization 88 copolymers, random and block, of
oxygen index see critical oxygen index 74
oxymethylene, poly- see acetals electroplating of 86
foams ... 84
packaging 48, 93 impact-modified 72, 73
painting (see also surface coating) 7, 51 MFI test and 73
paris on 13 thermal degradation of 73
permeation 6, 103, 134
permittivity 5 quinone methides 150
phenolformaldehyde (PF) plastics 70,
146, 148, 149 radiation, gamma-, resistance to 139
phenol formaldehyde foams 156 reaction injection moulding 35, 46, 184
phenolformaldehyde sheet moulding rear light assembly 63
compound 157 records, high-fidelity 132
phenylene oxide, poly- recovered strain 28
blends of with PS 56 reduced time 28
foams 58 refractive index 5
phenylene sulphide, poly- 144 refrigerators
reinforced 144 foam insulation for 182
INDEX 197
liners for 51 styrene - PPO foams 58

reinforced plastics 36, 38, 164 sulphones, poly- 140
resols 149, 156 'Udel' 141
rotational moulding 13, 34, 41- 5,92,94 polyethersulphone 141
polydiphenylsulphone 141
saucepan handles 152 supercooling 74, 88, 117
scattering of light 5 surface coatings 7, 164, 173, 186, 191
sealer bed pocket 109 switches, direction-indicating 122, 155
seals 82, 191
seating texture, crystalline 21
kitchen 186 thermal conductivity 4
stackable 81, 82 thermal degradation 124, 139, 177
upholstery for 180 thermal expansion 4, 179
sequential polymerization 74 thermoforming 15, 34, 41, 51
shape stabilization 6, 8, 9, 20 thermoplastic elastomers 82
shaping thermoplastics
of cross-linking plastics 9 processing of 8, 10
primary 8 product design of 35
secondary 8, 13 thermosetting plastiCs, product design
shear viscosity 8 of 35
sheet moulding compound 157, 167 - 9 time dependence 2
shoe components 82, 116, 133, 177, 186 time, reduced 28
shot weight II tolerances and dimensional control 39,
shrinkage 4, 20, 39, 48, 51 56, 58, 115, 149
silicone resins 148 toughness 105
sizing die II fracture 32, 33
solid-phase pressure forming 80 tracking resistance 160
solubility (of fluids in polymer) 6 transfer moulding 17, 151
spray foam 156, 182 transparency 5, 68, 10 I
spray lay-up 17,35,41-3,167 tubular film 13
stabilization (against UV radiation) 7, 178
stabilizers (thermal) for PVC 125 ultraviolet stabilization 7
strain-limited design 27 UV-stable antioxidants 73, 178
strength unsaturated polyester resin 148, 163
electrical 5 glass fibre-reinforced 164
impact 28, 29, 54, 57, 62, 67, 73, 105 urea formaldehyde plastics 158
long-term 27, 61, 68, 91, 127 cross-linking in 159
vs. temperature 142 foams 160
vs. time in water 122 urethanes, poly- 174
stretch-blown bottles 15, 86, 112 foams, flexible 180
stress concentration 28, 30, 74 rigid 182
stress intensity factor 32 self-skin semi-flexible 186, 187
stress vs. strain 25, 105 self-skin rigid 186, 187
styrene plastics (PS) 47 reaction injection moulded 188
blends with poly(phenylene oxide) 56 thermoplastics 190
crystal grades 47 thermosetting 189
high-impact 49 usage of plastics materials 24
use of solvent adhesives with 51
styrene copolymers vacuum cleaners 56
ABS plastics 54 components of 70
acrylonitrile 52 vinyl acetate copolymer
butadiene 52 with ethylene 100
block (butadiene) 53 with vinyl chloride 132
198 INDEX
vinyl chloride, poly- 124 vinyltrichlorsilane 165

blends (NBR, EVAC, PU) 133 viscosity, shear 8
copolymers of 132 washing machine drum 84 - 5
as monomer 124 water absorption
plasticized (pastes, plastisols) by MF 161
128 by polyamides 104
vinylidene chloride, poly- 65, 133 by polyesters III
copolymers of 133
with acrylonitrile 134 Ziegler catalyst 88
with vinyl chloride 134 Ziegler - Natta catalyst 72

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~ WOlVERHAMPTON

Telford Learning Centre

Telephone Renewals: 01902 321333 or 0845 408 1631

BLACKIE ACADEMIC & PROFESSIONAL

London· Glasgow· New York· Tokyo· Melbourne· Madras

Chapman & Hall, 2-6 Boundary Row, London SE1 8HN, UK

First edition 1982

© 1988 B1ackie & Son Ltd

Typeset by Thomson Press (India) Ltd, New Delhi

ISBN 978-0-7514-0162-2 ISBN 978-94-011-7614-9 (eBook)

4 Other amorphous thermoplastics 60

6 Other polyolefin plastics 87

7 Other crystalline thermoplastics 103

8 Vinyl chloride plastics 124

9 Speciality therntoplastics 135

10 Cross-linked plastics 148

11 Polyurethane plastics 174

1.2 Structure and properties of plastics

'Properties' provide quantitative information on the response of a material

1.2.1 Mechanical properties

1.2.2 Thermal properties

1.2.4 Optical properties

1.2.5 Melt properties

application of heat, the shaped part being stabilized in form by cooling; no

1.2.6 Chemical properties

1.4 Processing of plastics

1.4.1 Thermoplastics processing

1.4.3 Shaping of cross-linking plastics

particularly important and give composites of considerably enhanced pro-

1.5 Practical methods of processing

1.5.1 Thermoplastics processing

sizing die cy li nder screw

L.. ,,;,g zonJ plasticizing

Figure 1.3 Ex truder

(i) Injection moulding. Plastics material in granular or powder form is fed

cavity injection cylinder

mou ld screw rotat ing unit

Figure 1.4 Injection moulder

the shot weight for PP is

Figure 1.5 Calender

Important methods of secondary shaping based on melt extrusion are outlined

to haul -off unit

vertical die --~~-----"'" extruder

Figure 1.6 Bl own fi lm - tubula r process

(vi) Injection blow moulding. In an analogous process, injection moulded

(vii) Thermoforming. This is a secondary shaping process which uses sheet

Figure 1.8 Thermoforming

1.5.2 Processing methods for cross-linking plastics

(i) High-pressure moulding. Important methods include the following

mould open mou ld closed

thermal insu lating plate top half

thermal insulating plate bottom half

(ii) Low-pressure moulding. Methods have been developed particularly for

(iii) Dual component dispensing techniques. Many thermosetting plastics,

REC I RCULA T I ON REC I RCLLAT I ON

I~ RECIRCLl..AT ION D I SPENSe:',

other systems (compare to approximately 1500 bars for injection moulding

1.6 Interactions between shaping process and plastics materials

(ii) Crystallinity. The crystallinity level attained on cooling a plastics melt

(iii) Crystalline texture. Cooling of a plastics melt can only be accomplished

Polymer manuJacturing and processing

Design is an exercise embracing many considerations: mechanical perfor-

2.1 Engineering design

Table 2.1 Usage and mass cost of plastics materials

o~ ~ ~ ~ ~